Production method for solid catalyst component for polymerizing olefins, catalyst for polymerizing olefins, and production method for polymerized olefins

ABSTRACT

A method produces a novel solid catalyst component for olefin polymerization that achieves excellent olefin polymerization activity and activity with respect to hydrogen during polymerization, and can produce an olefin polymer that exhibits a high MFR, high stereoregularity, and excellent rigidity. The method includes a first step that brings a magnesium compound, a tetravalent titanium halide compound, and one or more first internal electron donor compounds into contact with each other to effect a reaction, followed by washing; a second step that brings one or more second internal electron donor compounds into contact with a product obtained by the first step to effect a reaction; and a third step that brings a tetravalent titanium halide compound and one or more third internal electron donor compounds into contact with a product obtained by the second step to effect a reaction.

TECHNICAL FIELD

The present invention relates to a method for producing a solid catalystcomponent for olefin polymerization, a method for producing an olefinpolymerization catalyst, and a method for producing an olefin polymer.

BACKGROUND ART

An olefin (e.g., propylene) has been polymerized using an olefinpolymerization catalyst. The resulting olefin polymer may be melted,molded using a molding machine, a stretching machine, or the like, andused for a variety of applications (e.g., automotive parts, homeappliance parts, containers, and films).

A solid catalyst component that includes magnesium, titanium, anelectron donor compound, and a halogen atom as essential components hasbeen known as a component of the olefin polymerization catalyst. Anumber of olefin polymerization catalysts have been proposed thatinclude the solid catalyst component, an organoaluminum compound, and anorganosilicon compound.

An olefin polymer has been desired that exhibits higher flowability(melt flow rate (MFR)) when molded using a molding machine, a stretchingmachine, or the like.

The MFR of an olefin polymer depends largely on the molecular weight ofthe olefin polymer, and an olefin polymer having a low molecular weighttends to have a high MFR. Therefore, the molecular weight of an olefinpolymer is normally reduced by adding a large amount of hydrogen duringpolymerization in order to obtain an olefin polymer having a high MFR.

In recent years, an olefin polymer that has a high MFR, highstereoregularity, a reduced thickness, and high physical strength (i.e.,excellent rigidity) has been desired for producing large home applianceparts and automotive parts (particularly a bumper).

In view of the above situation, the applicant of the present applicationproposed an olefin polymerization catalyst and an olefin polymerizationmethod using the olefin polymerization catalyst, the olefinpolymerization catalyst including a solid catalyst component, anorganoaluminum compound, and an organosilicon compound, the solidcatalyst component being obtained by bringing a magnesium compound, atetravalent titanium halide compound, a malonic acid diester (internalelectron donor compound), and a phthalic acid diester (internal electrondonor compound) into contact with each other (see Patent Document 1(JP-A-2004-107462)).

RELATED-ART DOCUMENT Patent Document

-   Patent Document 1: JP-A-2004-107462

SUMMARY OF THE INVENTION Technical Problem

The olefin polymerization catalyst disclosed in Patent Document 1exhibits excellent activity with respect to hydrogen as compared withknown polymerization catalysts, and an olefin polymer obtained using thesolid catalyst component disclosed in Patent Document 1 exhibits highflowability (MFR) when melted, and is particularly useful when producinga large molded article by injection molding or the like.

According to further studies conducted by the inventors of theinvention, however, it was found that it is necessary to increase theamount of each internal electron donor compound in order to obtain asolid catalyst component having the desired internal electron donorcompound content by simultaneously bringing two or more differentinternal electron donor compounds into contact with the other componentsto effect a reaction. As a result, a complex of excess internal electrondonor compound and the tetravalent titanium halide compound is easilyformed, and the polymerization activity and the stereoregularity of theresulting olefin polymer easily decrease when using the resulting solidcatalyst component as a component of an olefin polymerization catalyst.

Moreover, an olefin polymerization catalyst that can produce an olefinpolymer that exhibits higher rigidity has been desired.

When producing a large molded article by injection molding or the like,it may be necessary to use a copolymer of two or more α-olefins (e.g.,propylene and ethylene) instead of a homopolymer of a single olefin(e.g., propylene).

Therefore, a solid catalyst component for olefin polymerization and anolefin polymerization catalyst that exhibit excellent sustainability ofpolymerization activity have been desired, thus ensuring that thepolymerization activity can be maintained for a long time whenpolymerizing a single olefin (e.g., propylene), and can also bemaintained for a long time when subjecting two or more olefins tocopolymerization or multistep polymerization.

However, when propylene and another α-olefin are copolymerized by amultistep polymerization process using a known catalyst, for example,the polymerization activity significantly decreases duringcopolymerization in the second or subsequent step when a polymer havinghigh stereoregularity is produced by first-step propylene polymerization(homopolymerization).

In view of the above situation, an object of the invention is to providea method for producing a novel solid catalyst component for olefinpolymerization that achieves excellent olefin polymerization activityand activity with respect to hydrogen during polymerization whenhomopolymerizing or copolymerizing an olefin, and can produce an olefinpolymer that exhibits a high MFR, high stereoregularity, and excellentrigidity while achieving high sustainability of polymerization activity,and also provide an olefin polymerization catalyst and a method forproducing an olefin polymer.

Solution to Problem

The inventors conducted extensive studies in order to achieve the aboveobject, and found that the above object can be achieved by producing asolid catalyst component for olefin polymerization by performing a firststep that brings a magnesium compound, a tetravalent titanium halidecompound, and one or more first internal electron donor compounds intocontact with each other to effect a reaction, followed by washing, asecond step that brings one or more second internal electron donorcompounds into contact with a product obtained by the first step toeffect a reaction, and a third step that brings a tetravalent titaniumhalide compound and a third internal electron donor compound intocontact with a product obtained by the second step to effect a reaction,preparing an olefin polymerization catalyst using the solid catalystcomponent, and reacting an olefin using the olefin polymerizationcatalyst. This finding has led to the completion of the invention.

Several aspects of the invention provide the following.

(1) A method for producing a solid catalyst component for olefinpolymerization including:

a first step that brings a magnesium compound, a tetravalent titaniumhalide compound, and one or more first internal electron donor compoundsinto contact with each other to effect a reaction, followed by washing;

a second step that brings one or more second internal electron donorcompounds into contact with a product obtained by the first step toeffect a reaction; and

a third step that brings a tetravalent titanium halide compound and oneor more third internal electron donor compounds into contact with aproduct obtained by the second step to effect a reaction.

(2) The method for producing a solid catalyst component for olefinpolymerization according to (1), wherein the second internal electrondonor compound is used so that the ratio “molar quantity of the secondinternal electron donor compound/molar quantity of the magnesiumcompound” is 0.001 to 10.(3) The method for producing a solid catalyst component for olefinpolymerization according to (1) or (2), wherein the third internalelectron donor compound is used so that the ratio “molar quantity of thethird internal electron donor compound/molar quantity of the magnesiumcompound” is 0.001 to 10.(4) The method for producing a solid catalyst component for olefinpolymerization according to any one of (1) to (3), wherein the firstinternal electron donor compound, the second internal electron donorcompound, and the third internal electron donor compound are used sothat the relationship “molar quantity of the first internal electrondonor compound>molar quantity of the second internal electron donorcompound≧molar quantity of the third internal electron donor compound”is satisfied.(5) The method for producing a solid catalyst component for olefinpolymerization according to any one of (1) to (4), wherein the secondinternal electron donor compound is brought into contact with theproduct obtained by the first step in an inert organic solvent for whicha tetravalent titanium halide compound content is controlled to 0 to 5mass %.(6) An olefin polymerization catalyst produced by bringing a solidcatalyst component for olefin polymerization obtained by the method forproducing a solid catalyst component for olefin polymerization accordingto any one of (1) to (5), an organoaluminum compound represented by thefollowing general formula (I), and an external electron donor compoundinto contact with each other,

R¹ _(p)AlQ_(3-p)  (I)

wherein R¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogenatom or a halogen atom, and p is a real number that satisfies 0<p≦3.(7) The olefin polymerization catalyst according to (6), wherein theexternal electron donor compound is one or more organosilicon compoundsselected from an organosilicon compound represented by the followinggeneral formula (II) and an organosilicon compound represented by thefollowing general formula (III),

R² _(q)Si(OR³)_(4-q)  (II)

wherein R² is an alkyl group having 1 to 12 carbon atoms, a cycloalkylgroup having 3 to 12 carbon atoms, a phenyl group, a vinyl group, anallyl group, or an aralkyl group, provided that a plurality of R² areeither identical or different when a plurality of R² are present, R³ isan alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, or anaralkyl group, provided that a plurality of R³ are either identical ordifferent when a plurality of R³ are present, and q is an integer from 0to 3,

(R⁴R⁵N)_(s)SiR⁶ _(4-s)  (III)

wherein R⁴ and R⁵ are a hydrogen atom, a linear alkyl group having 1 to20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, avinyl group, an allyl group, an aralkyl group, a cycloalkyl group having3 to 20 carbon atoms, or an aryl group, provided that R⁴ and R⁵ areeither identical or different, and optionally bond to each other to forma ring, R⁶ is a linear alkyl group having 1 to 20 carbon atoms, abranched alkyl group having 3 to 20 carbon atoms, a vinyl group, anallyl group, an aralkyl group, a linear or branched alkoxy group having1 to 20 carbon atoms, a vinyloxy group, an allyloxy group, a cycloalkylgroup having 3 to 20 carbon atoms, an aryl group, or an aryloxy group,provided that a plurality of R⁶ are either identical or different when aplurality of R⁶ are present, and s is an integer from 1 to 3.(8) A method for producing an olefin polymer including polymerizing anolefin in the presence of the olefin polymerization catalyst accordingto (6) or (7).

In particular, several aspects of the invention provide the following.

(1)′ A method for producing a solid catalyst component for olefinpolymerization including:

a first step that brings a magnesium compound, a tetravalent titaniumhalide compound, and one or more first internal electron donor compoundsinto contact with each other to effect a reaction, followed by washing;

a second step that brings one or more second internal electron donorcompounds into contact with a product obtained by the first step toeffect a reaction; and a third step that brings a tetravalent titaniumhalide compound and one or more third internal electron donor compoundsinto contact with a product obtained by the second step to effect areaction.

(2)′ The method for producing a solid catalyst component for olefinpolymerization according to (1)′, wherein the second internal electrondonor compound is used so that the ratio “molar quantity of the secondinternal electron donor compound/molar quantity of the magnesiumcompound” is 0.001 to 10.(3)′ The method for producing a solid catalyst component for olefinpolymerization according to (1)′, wherein the third internal electrondonor compound is used so that the ratio “molar quantity of the thirdinternal electron donor compound/molar quantity of the magnesiumcompound” is 0.001 to 10.(4)′ The method for producing a solid catalyst component for olefinpolymerization according to (1)′, wherein the first internal electrondonor compound, the second internal electron donor compound, and thethird internal electron donor compound are used so that the relationship“molar quantity of the first internal electron donor compound>molarquantity of the second internal electron donor compound≧molar quantityof the third internal electron donor compound” is satisfied.(5)′ The method for producing a solid catalyst component for olefinpolymerization according to (1)′, wherein the second internal electrondonor compound is brought into contact with the product obtained by thefirst step in an inert organic solvent for which a tetravalent titaniumhalide compound content is controlled to 0 to 5 mass %.(6)′ An olefin polymerization catalyst produced by bringing a solidcatalyst component for olefin polymerization obtained by the method forproducing a solid catalyst component for olefin polymerization accordingto any one of (1)′ to (5)′, an organoaluminum compound represented bythe following general formula (I), and an external electron donorcompound into contact with each other,

R¹ _(p)AlQ_(3-p)  (I)

wherein R¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogenatom or a halogen atom, and p is a real number that satisfies 0<p≦3.(7)′ The olefin polymerization catalyst according to (6)′, wherein theexternal electron donor compound is one or more organosilicon compoundsselected from an organosilicon compound represented by the followinggeneral formula (II) and an organosilicon compound represented by thefollowing general formula (III),

R² _(q)Si(OR³)_(4-q)  (II)

wherein R² is an alkyl group having 1 to 12 carbon atoms, a cycloalkylgroup having 3 to 12 carbon atoms, a phenyl group, a vinyl group, anallyl group, or an aralkyl group, provided that a plurality of R² areeither identical or different when a plurality of R² are present, R³ isan alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, or anaralkyl group, provided that a plurality of R³ are either identical ordifferent when a plurality of R³ are present, and q is an integer from 0to 3,

(R⁴R⁵N)_(s)SiR⁶ _(4-s)  (III)

wherein R⁴ and R⁵ are a hydrogen atom, a linear alkyl group having 1 to20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, avinyl group, an allyl group, an aralkyl group, a cycloalkyl group having3 to 20 carbon atoms, or an aryl group, provided that R⁴ and R⁵ areeither identical or different, and optionally bond to each other to forma ring, R⁶ is a linear alkyl group having 1 to 20 carbon atoms, abranched alkyl group having 3 to 20 carbon atoms, a vinyl group, anallyl group, an aralkyl group, a linear or branched alkoxy group having1 to 20 carbon atoms, a vinyloxy group, an allyloxy group, a cycloalkylgroup having 3 to 20 carbon atoms, an aryl group, or an aryloxy group,provided that a plurality of R⁶ are either identical or different when aplurality of R⁶ are present, and s is an integer from 1 to 3.(8)′ A method for producing an olefin polymer including polymerizing anolefin in the presence of the olefin polymerization catalyst accordingto (6)′.(9)′ A method for producing an olefin polymer including polymerizing anolefin in the presence of the olefin polymerization catalyst accordingto (7)′.

Advantageous Effects of the Invention

The aspects of the invention thus provide a novel solid catalystcomponent for olefin polymerization that achieves excellent olefinpolymerization activity and activity with respect to hydrogen duringpolymerization when homopolymerizing or copolymerizing an olefin, andcan produce an olefin polymer that exhibits a high MFR, highstereoregularity, and excellent rigidity while achieving highsustainability of polymerization activity, and also provide a method forproducing an olefin polymerization catalyst and a method for producingan olefin polymer.

DESCRIPTION OF EMBODIMENTS

A method for producing a solid catalyst component for olefinpolymerization (hereinafter may be referred to as “production method”)according to one embodiment of the invention is described below.

The method for producing a solid catalyst component for olefinpolymerization according to one embodiment of the invention includes: afirst step that brings a magnesium compound, a tetravalent titaniumhalide compound, and one or more first internal electron donor compoundsinto contact with each other to effect a reaction, followed by washing;a second step that brings one or more second internal electron donorcompounds into contact with a product obtained by the first step toeffect a reaction; and a third step that brings a tetravalent titaniumhalide compound and one or more third internal electron donor compoundsinto contact with a product obtained by the second step to effect areaction.

First Step

The magnesium compound used in connection with the method for producinga solid catalyst component for olefin polymerization according to oneembodiment of the invention may be one or more magnesium compoundsselected from a dialkoxymagnesium, a magnesium dihalide, analkoxymagnesium halide, and the like.

Among these magnesium compounds, a dialkoxymagnesium and a magnesiumdihalide are preferable. Specific examples of the dialkoxymagnesium andthe magnesium dihalide include dimethoxymagnesium, diethoxymagnesium,dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium,ethoxypropoxymagnesium, butoxyethoxymagnesium, magnesium dichloride,magnesium dibromide, magnesium diiodide, and the like. Among these,diethoxymagnesium and magnesium dichloride are particularly preferable.

The dialkoxymagnesium may be a dialkoxymagnesium obtained by reactingmagnesium metal with an alcohol in the presence of a halogen, ahalogen-containing metal compound, or the like.

It is preferable to use a granular or powdery dialkoxymagnesium whenimplementing the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention. Thedialkoxymagnesium may have an indefinite shape or a spherical shape.

When a spherical dialkoxymagnesium is used, the resulting polymer powderhas a better (more spherical) particle shape and a narrower particlesize distribution. This makes it possible to improve the handlingcapability of the polymer powder produced during polymerization, andeliminate occurrence of a problem (e.g., clogging) due to a fine powderincluded in the polymer powder.

The spherical dialkoxymagnesium need not necessarily have a perfectspherical shape, but may have an elliptical shape or a potato-likeshape. It is preferable that the dialkoxymagnesium particles have asphericity of 3 or less, more preferably 1 to 2, and still morepreferably 1 to 1.5.

Note that the term “sphericity” used herein in connection with thedialkoxymagnesium particles refers to a value obtained by photographing500 or more dialkoxymagnesium particles using a scanning electronmicroscope, processing the photographed particles using image analysissoftware to determine the area S and the circumferential length L ofeach dialkoxymagnesium particle, calculating the sphericity of eachdialkoxymagnesium particle using the following expression, andcalculating the arithmetic mean value thereof. The sphericity is closeto 1 when the shape of the particle is close to a true circle.

Sphericity of each dialkoxymagnesium particle=4π×S÷L ²

The average particle size D50 (i.e., the particle size at 50% in thecumulative volume particle size distribution) of the dialkoxymagnesiummeasured using a laser diffraction/scattering particle size distributionanalyzer is preferably 1 to 200 μm, and more preferably 5 to 150 μm.

The average particle size of the spherical dialkoxymagnesium ispreferably 1 to 100 μm, more preferably 5 to 60 μm, and still morepreferably 10 to 50 μm.

It is preferable that the dialkoxymagnesium have a narrow particle sizedistribution, and have a low fine particle content and a low coarseparticle content.

Specifically, it is preferable that the dialkoxymagnesium have a contentof particles having a particle size (measured using a laserdiffraction/scattering particle size distribution analyzer) equal to orsmaller than 5 μm of 20% or less, and more preferably 10% or less. It ispreferable that the dialkoxymagnesium have a content of particles havinga particle size (measured using a laser diffraction/scattering particlesize distribution analyzer) equal to or larger than 100 μm of 10% orless, and more preferably 5% or less.

The particle size distribution ln(D90/D10) (where, D90 is the particlesize at 90% in the cumulative volume particle size distribution, and D10is the particle size at 10% in the cumulative volume particle sizedistribution) of the dialkoxymagnesium is preferably 3 or less, and morepreferably 2 or less.

The spherical dialkoxymagnesium may be produced using the methoddisclosed in JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391,JP-A-8-73388, or the like.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,it is preferable that the magnesium compound be used in the form of asolution or a suspension when subjected to the reaction. When themagnesium compound is used in the form of a solution or a suspension,the reaction proceeds advantageously.

When the magnesium compound is solid, the magnesium compound may bedissolved in a solvent that can dissolve the magnesium compound toprepare a magnesium compound solution, or may be suspended in a solventthat cannot dissolve the magnesium compound to prepare a magnesiumcompound suspension.

When the magnesium compound is liquid, the magnesium compound may beused directly, or may be dissolved in a solvent that can dissolve themagnesium compound to prepare a magnesium compound solution.

Examples of a compound that can dissolve the solid magnesium compoundinclude at least one compound selected from the group consisting of analcohol, an ether, and an ester.

Specific examples of the compound that can dissolve the solid magnesiumcompound include alcohols having 1 to 18 carbon atoms, such as methanol,ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol,dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethylalcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol, andethylene glycol, halogen-containing alcohols having 1 to 18 carbonatoms, such as trichloromethanol, trichloroethanol, andtrichlorohexanol, ethers having 2 to 20 carbon atoms, such as methylether, ethyl ether, isopropyl ether, butyl ether, amyl ether,tetrahydrofuran, ethyl benzyl ether, dibutyl ether, anisole, anddiphenyl ether, metal acid esters such as tetraethoxytitanium,tetra-n-propoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium,tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium, andthe like. Among these, alcohols such as ethanol, propanol, butanol, and2-ethylhexanol are preferable, and 2-ethylhexanol is particularlypreferable.

Examples of a medium that cannot dissolve the solid magnesium compoundinclude one or more solvents selected from a saturated hydrocarbonsolvent and an unsaturated hydrocarbon solvent that do not dissolve amagnesium compound.

The saturated hydrocarbon solvent and the unsaturated hydrocarbonsolvent are safe, and have high industrial versatility. Examples of thesaturated hydrocarbon solvent and the unsaturated hydrocarbon solventinclude linear or branched aliphatic hydrocarbon compounds having aboiling point of 50 to 200° C., such as hexane, heptane, decane, andmethylheptane, alicyclic hydrocarbon compounds having a boiling point of50 to 200° C., such as cyclohexane, ethylcyclohexane, anddecahydronaphthalene, and aromatic hydrocarbon compounds having aboiling point of 50 to 200° C., such as toluene, xylene, andethylbenzene. Among these, linear aliphatic hydrocarbon compounds havinga boiling point of 50 to 200° C., such as hexane, heptane, and decane,and aromatic hydrocarbon compounds having a boiling point of 50 to 200°C., such as toluene, xylene, and ethylbenzene, are preferable.

The tetravalent titanium halide compound used in the first step includedin the method for producing a solid catalyst component for olefinpolymerization according to one embodiment of the invention is notparticularly limited, but is preferably one or more compounds selectedfrom a titanium halide and an alkoxytitanium halide represented by thefollowing general formula (IV).

Ti(OR⁷)_(r)X_(4-r)  (IV)

wherein R⁷ is an alkyl group having 1 to 4 carbon atoms, X is a halogenatom (e.g., chlorine atom, bromine atom, or iodine atom), and r is aninteger from 0 to 3.

Examples of the titanium halide include titanium tetrahalides such astitanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.

Examples of the alkoxytitanium halide include methoxytitaniumtrichloride, ethoxytitanium trichloride, propoxytitanium trichloride,n-butoxytitanium trichloride, dimethoxytitanium dichloride,diethoxytitanium dichloride, dipropoxytitanium dichloride,di-n-butoxytitanium dichloride, trimethoxytitanium chloride,triethoxytitanium chloride, tripropoxytitanium chloride,tri-n-butoxytitanium chloride, and the like.

Among these, titanium tetrahalides are preferable, and titaniumtetrachloride is more preferable.

These titanium compounds may be used either alone or in combination.

One or more first internal electron donor compounds are used in thefirst step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention.

The first internal electron donor compound is preferably an organiccompound that includes an oxygen atom or nitrogen atom. The firstinternal electron donor compound may be one or more compounds selectedfrom an alcohol, a phenol, an ether, an ester, a ketone, an acid halide,an aldehyde, an amine, an amide, a nitrile, an isocyanate, anorganosilicon compound that includes an Si—O—C linkage or an Si—N—Clinkage, and the like.

An ether compound (e.g., monoether, diether, and ether carbonate) and anester (e.g., monocarboxylic acid ester and polycarboxylic acid ester)are more preferable as the first internal electron donor compound. Thefirst internal electron donor compound is still more preferably one ormore compounds selected from an aromatic polycarboxylic acid ester(e.g., aromatic dicarboxylic acid diester), an aliphatic polycarboxylicacid ester, an alicyclic polycarboxylic acid ester, a diether, and anether carbonate.

Examples of the aromatic dicarboxylic acid diester that may be used inconnection with the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the inventioninclude a compound represented by the following general formula (V).

(R⁸)_(j)C₆H_(4-j)(COOR⁹)(COOR¹⁰)  (V)

wherein R⁸ is an alkyl group having 1 to 8 carbon atoms or a halogenatom, R⁹ and R¹⁰ are an alkyl group having 1 to 12 carbon atoms,provided that R⁹ and R¹⁰ are either identical or different, and j, whichis the number of substituents R⁸, is 0, 1, or 2, provided that R⁸ areeither identical or different when j is 2.

R⁸ in the aromatic dicarboxylic acid diester represented by the generalformula (V) is a halogen atom or an alkyl group having 1 to 8 carbonatoms.

Examples of the halogen atom represented by R⁸ include one or more atomsselected from a fluorine atom, a chlorine atom, a bromine atom, and aniodine atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R⁸include one or more groups selected from a methyl group, an ethyl group,a n-propyl group, an isopropyl group, a n-butyl group, an isobutylgroup, a t-butyl group, a n-pentyl group, an isopentyl group, aneopentyl group, a n-hexyl group, an isohexyl group, a 2,2-dimethylbutylgroup, a 2,2-dimethylpentyl group, an isooctyl group, and a2,2-dimethylhexyl group.

R⁸ is preferably a methyl group, a bromine atom, or a fluorine atom, andmore preferably a methyl group or a bromine atom.

R⁹ and R¹⁰ in the aromatic dicarboxylic acid diester represented by thegeneral formula (V) are an alkyl group having 1 to 12 carbon atoms,provided that R⁹ and R¹⁰ are either identical or different.

Examples of the alkyl group having 1 to 12 carbon atoms include a methylgroup, an ethyl group, a n-propyl group, an isopropyl group, a n-butylgroup, an isobutyl group, a t-butyl group, a n-pentyl group, anisopentyl group, a neopentyl group, a n-hexyl group, an isohexyl group,a 2,2-dimethylbutyl group, a 2,2-dimethylpentyl group, an isooctylgroup, a 2,2-dimethylhexyl group, a n-nonyl group, an isononyl group, an-decyl group, an isodecyl group, and a n-dodecyl group. Among these, anethyl group, a n-butyl group, an isobutyl group, a t-butyl group, aneopentyl group, an isohexyl group, and an isooctyl group (particularlyan ethyl group, a n-propyl group, a n-butyl group, an isobutyl group,and a neopentyl group) are preferable.

j (i.e., the number of substituents R⁸) in the aromatic dicarboxylicacid diester represented by the general formula (V) is 0, 1, or 2,provided that R⁸ (two R⁸) are either identical or different when j is 2.

The compound represented by the general formula (V) is a phthalic aciddiester when j is 0, and is a substituted phthalic acid diester when jis 1 or 2.

When j is 1, it is preferable that R⁸ in the aromatic dicarboxylic aciddiester represented by the general formula (V) substitute the hydrogenatom at position 3, 4, or 5 of the benzene ring.

When j is 2, it is preferable that R⁸ in the aromatic dicarboxylic aciddiester represented by the general formula (V) substitute the hydrogenatom at position 4 or 5 of the benzene ring.

Specific examples of the aromatic dicarboxylic acid diester representedby the general formula (V) include phthalic acid diesters such asdimethyl phthalate, diethyl phthalate, di-n-propyl phthalate,diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate,di-n-hexyl phthalate, dithexyl phthalate, methylethyl phthalate,(ethyl)n-propyl phthalate, ethylisopropyl phthalate, (ethyl)n-butylphthalate, ethylisobutyl phthalate, (ethyl)n-pentyl phthalate,ethylisopentyl phthalate, ethylneopentyl phthalate, and (ethyl)n-hexylphthalate, halogen-substituted phthalic acid diesters such as diethyl4-chlorophthalate, di-n-propyl 4-chlorophthalate, diisopropyl4-chlorophthalate, di-n-butyl 4-chlorophthalate, diisobutyl4-chlorophthalate, diethyl 4-bromophthalate, di-n-propyl4-bromophthalate, diisopropyl 4-bromophthalate, di-n-butyl4-bromophthalate, and diisobutyl 4-bromophthalate, alkyl-substitutedphthalic acid diesters such as diethyl 4-methylphthalate, di-n-propyl4-methylphthalate, diisopropyl 4-methylphthalate, di-n-butyl4-methylphthalate, and diisobutyl 4-methylphthalate, and the like.

Among these, diethyl phthalate, di-n-propyl phthalate, di-n-butylphthalate, diisobutyl phthalate, di-n-pentyl phthalate, diisopentylphthalate, dineopentyl phthalate, di-n-hexyl phthalate, (ethyl)n-propylphthalate, ethylisopropyl phthalate, (ethyl)n-butyl phthalate,ethylisobutyl phthalate, diethyl 4-methylphthalate, di-n-propyl4-methylphthalate, diisobutyl 4-methylphthalate, diisobutyl4-bromophthalate, diisopentyl 4-bromophthalate, dineopentyl4-bromophthalate, and the like are preferable, and diethyl phthalate,di-n-propyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,(ethyl)n-propyl phthalate, ethylisopropyl phthalate, (ethyl)n-butylphthalate, ethylisobutyl phthalate, diethyl 4-methylphthalate,di-n-propyl 4-methylphthalate, diisobutyl 4-methylphthalate, diisobutyl4-bromophthalate, diisopentyl 4-bromophthalate, and dineopentyl4-bromophthalate are more preferable.

Examples of the aliphatic polycarboxylic acid ester that may be used asthe first internal electron donor compound include a saturated aliphaticpolycarboxylic acid ester and an unsaturated aliphatic polycarboxylicacid ester.

Examples of the saturated aliphatic polycarboxylic acid ester include amalonic acid diester, a succinic acid diester, a fumaric acid diester,an adipic acid diester, a glutaric acid diester, and the like. Thesaturated aliphatic polycarboxylic acid ester is preferably onecompound, or two or more compounds, selected from a malonic aciddiester, an alkyl-substituted malonic acid diester, analkylene-substituted malonic acid diester, and a succinic acid diester.

Examples of the unsaturated aliphatic polycarboxylic acid ester includea maleic acid diester and the like. The unsaturated aliphaticpolycarboxylic acid ester is preferably one compound, or two or morecompounds, selected from a maleic acid diester and an alkyl-substitutedmaleic acid diester.

Examples of the succinic acid diester that may be used as the firstinternal electron donor compound include diethyl succinate, dibutylsuccinate, diethyl methylsuccinate, diethyl 2,3-diisopropylsuccinate,and the like. Among these, diethyl succinate and diethyl2,3-diisopropylsuccinate are preferable.

Examples of the maleic acid diester that may be used as the firstinternal electron donor compound include diethyl maleate, di-n-propylmaleate, diisopropyl maleate, di-n-butyl maleate, diisobutyl maleate,di-n-pentyl maleate, dineopentyl maleate, dihexyl maleate, dioctylmaleate, and the like. Among these, diethyl maleate, di-n-butyl maleate,and diisobutyl maleate are preferable.

Examples of the alkyl-substituted maleic acid diester that may be usedas the first internal electron donor compound include diethylisopropylbromomaleate, diethyl butylbromomaleate, diethylisobutylbromomaleate, diethyl diisopropylmaleate, diethyldibutylmaleate, diethyl diisobutylmaleate, diethyl diisopentylmaleate,diethyl isopropylisobutylmaleate, dimethyl isopropylisopentylmaleate,diethyl(3-chloro-n-propyl)maleate, diethyl bis(3-bromo-n-propyl)maleate,dibutyl dimethylmaleate, dibutyl diethylmaleate, and the like. Amongthese, dibutyl dimethylmaleate, dibutyl diethylmaleate, and diethyldiisobutylmaleate are preferable.

Examples of the malonic acid diester that may be used as the firstinternal electron donor compound include dimethyl malonate, diethylmalonate, di-n-propyl malonate, diisopropyl malonate, di-n-butylmalonate, diisobutyl malonate, dineopentyl malonate, and the like. Amongthese, dimethyl malonate, diethyl malonate, and diisobutyl malonate arepreferable.

A substituted malonic acid diester is preferable as the first internalelectron donor compound.

Examples of the substituted malonic acid diester that may be used as thefirst internal electron donor compound include an alkyl-substitutedmalonic acid diester, a halogen-substituted malonic acid diester, analkyl halide-substituted malonic acid diester, and the like. Amongthese, an alkyl-substituted malonic acid diester and ahalogen-substituted malonic acid diester are preferable, and analkyl-substituted malonic acid diester is more preferable.

Examples of the alkyl-substituted malonic acid diester include one ormore compounds selected from monoalkylmalonic acid diesters such asdimethyl methylmalonate, diethyl methylmalonate, dipropylmethylmalonate, diisopropyl methylmalonate, dibutyl methylmalonate,diisobutyl methylmalonate, dineopentyl methylmalonate, dimethylethylmalonate, diethyl ethylmalonate, dipropyl ethylmalonate,diisopropyl ethylmalonate, dibutyl ethylmalonate, diisobutylethylmalonate, dineopentyl ethylmalonate, dimethyl propylmalonate,diethyl isopropylmalonate, dipropyl isopropylmalonate, diisopropylisopropylmalonate, dibutyl isopropylmalonate, diisobutylisopropylmalonate, dineopentyl isopropylmalonate, dimethylisobutylmalonate, diethyl isobutylmalonate, dipropyl isobutylmalonate,diisopropyl isobutylmalonate, dibutyl isobutylmalonate, diisobutylisobutylmalonate, dineopentyl isobutylmalonate, dimethylisopentylmalonate, diethyl isopentylmalonate, dipropylisopentylmalonate, diisopropyl isopentylmalonate, dibutylisopentylmalonate, diisobutyl isopentylmalonate, and dineopentylisopentylmalonate, dialkylmalonic acid diesters such as dimethylcyclopentylmethylmalonate, diethyl cyclopentylmethylmalonate, dipropylcyclopentylmethylmalonate, diisopropyl cyclopentylmethylmalonate,dibutyl cyclopentylmethylmalonate, diisobutyl cyclopentylmethylmalonate,dineopentyl cyclopentylmethylmalonate, dimethylcyclopentylethylmalonate, diethyl cyclopentylethylmalonate, dipropylcyclopentylethylmalonate, diisopropyl cyclopentylethylmalonate, dibutylcyclopentylethylmalonate, diisobutyl cyclopentylethylmalonate,dineopentyl cyclopentylethylmalonate, dimethylcyclopentylpropylmalonate, diethyl cyclopentylisopropylmalonate,dipropyl cyclopentylisopropylmalonate, diisopropylcyclopentylisopropylmalonate, dibutyl cyclopentylisopropylmalonate,diisobutyl cyclopentylisopropylmalonate, dineopentylcyclopentylisopropylmalonate, dimethyl cyclopentylisobutylmalonate,diethyl cyclopentylisobutylmalonate, dipropylcyclopentylisobutylmalonate, diisopropyl cyclopentylisobutylmalonate,dibutyl cyclopentylisobutylmalonate, diisobutylcyclopentylisobutylmalonate, dineopentyl cyclopentylisobutylmalonate,dimethyl cyclopentylisopentylmalonate, diethylcyclopentylisopentylmalonate, dipropyl cyclopentylisopentylmalonate,diisopropyl cyclopentylisopentylmalonate, dibutylcyclopentylisopentylmalonate, diisobutyl cyclopentylisopentylmalonate,dineopentyl cyclopentylisopentylmalonate, dimethylcyclohexylmethylmalonate, diethyl cyclohexylmethylmalonate, dipropylcyclohexylmethylmalonate, diisopropyl cyclohexylmethylmalonate, dibutylcyclohexylmethylmalonate, diisobutyl cyclohexylmethylmalonate,dineopentyl cyclohexylmethylmalonate, dimethyl cyclohexylethylmalonate,diethyl cyclohexylethylmalonate, dipropyl cyclohexylethylmalonate,diisopropyl cyclohexylethylmalonate, dibutyl cyclohexylethylmalonate,diisobutyl cyclohexylethylmalonate, dineopentyl cyclohexylethylmalonate,dimethyl cyclohexylpropylmalonate, diethyl cyclohexylisopropylmalonate,dipropyl cyclohexylisopropylmalonate, diisopropylcyclohexylisopropylmalonate, dibutyl cyclohexylisopropylmalonate,diisobutyl cyclohexylisopropylmalonate, dineopentylcyclohexylisopropylmalonate, dimethyl cyclohexylisobytylmalonate,diethyl isobutylmalonate, dipropyl cyclohexylisobutylmalonate,diisopropyl cyclohexylisobutylmalonate, dibutylcyclohexylisobutylmalonate, diisobutyl cyclohexylisobutylmalonate,dineopentyl cyclohexylisobutylmalonate, dimethylcyclohexylisopentylmalonate, diethyl cyclohexylisopentylmalonate,dipropyl cyclohexylisopentylmalonate, diisopropylcyclohexylisopentylmalonate, dibutyl cyclohexylisopentylmalonate,diisobutyl cyclohexylisopentylmalonate, dineopentylcyclohexylisopentylmalonate, dimethyl phenylmethylmalonate, diethylphenylmethylmalonate, dipropyl phenylmethylmalonate, diisopropylphenylmethylmalonate, dibutyl phenylmethylmalonate, diisobutylphenylmethylmalonate, dineopentyl phenylmethylmalonate, dimethylphenylethylmalonate, diethyl phenylethylmalonate, dipropylphenylethylmalonate, diisopropyl phenylethylmalonate, dibutylphenylethylmalonate, diisobutyl phenylethylmalonate, dineopentylphenylethylmalonate, dimethyl phenylpropylmalonate, diethylphenylisopropylmalonate, dipropyl phenylisopropylmalonate, diisopropylphenylisopropylmalonate, dibutyl phenylisopropylmalonate, diisobutylphenylisopropylmalonate, dineopentyl phenylisopropylmalonate, dimethylphenylisobutylmalonate, diethyl phenylisobutylmalonate, dipropylphenylisobutylmalonate, diisopropyl phenylisobutylmalonate, dibutylphenylisobutylmalonate, diisobutyl phenylisobutylmalonate, dineopentylphenylisobutylmalonate, dimethyl phenylisopentylmalonate, diethylphenylisopentylmalonate, dipropyl phenylisopentylmalonate, diisopropylphenylisopentylmalonate, dibutyl phenylisopentylmalonate, diisobutylphenylisopentylmalonate, dineopentyl phenylisopentylmalonate, dimethyldiisopropylmalonate, diethyl diisopropylmalonate, dipropyldiisopropylmalonate, diisopropyl diisopropylmalonate, dibutyldiisopropylmalonate, diisobutyl diisopropylmalonate, dineopentyldiisopropylmalonate, dimethyl diisobutylmalonate, diethyldiisobutylmalonate, dipropyl diisobutylmalonate, diisopropyldiisobutylmalonate, dibutyl diisobutylmalonate, diisobutyldiisobutylmalonate, dineopentyl diisobutylmalonate, dimethyldiisopentylmalonate, diethyl diisopentylmalonate, dipropyldiisopentylmalonate, diisopropyl diisopentylmalonate, dibutyldiisopentylmalonate, diisobutyl diisopentylmalonate, dineopentyldiisopentylmalonate, dimethyl isopropylisobutylmalonate, diethylisopropylisobutylmalonate, dipropyl isopropylisobutylmalonate,diisopropyl isopropylisobutylmalonate, dibutylisopropylisobutylmalonate, diisobutyl isopropylisobutylmalonate,dineopentyl isopropylisobutylmalonate, dimethylisopropylisopentylmalonate, diethyl isopropylisopentylmalonate, dipropylisopropylisopentylmalonate, diisopropyl isopropylisopentylmalonate,dibutyl isopropylisopentylmalonate, diisobutylisopropylisopentylmalonate, and dineopentyl isopropylisopentylmalonate,and alkylidenemalonic acid diesters such as dimethylpropylidenemalonate, diethyl propylidenemalonate, di-n-propylpropylidenemalonate, diisobutyl propylidenemalonate, di-n-butylpropylidenemalonate, dimethyl butylidenemalonate, diethylbutylidenemalonate, di-n-propyl butylidenemalonate, diisobutylbutylidenemalonate, di-n-butyl butylidenemalonate, dimethylpentylidenemalonate, diethyl pentylidenemalonate, di-n-propylpentylidenemalonate, diisobutyl pentylidenemalonate, di-n-butylpentylidenemalonate, dimethyl hexylidenemalonate, diethylhexylidenemalonate, di-n-propyl hexylidenemalonate, diisobutylhexylidenemalonate, di-n-butyl hexylidenemalonate,dimethyl(2-methylpropylidene)malonate,diethyl(2-methylpropylidene)malonate,di-n-propyl(2-methylpropylidene)malonate,diisobutyl(2-methylpropylidene)malonate,di-n-butyl(2-methylpropylidene)malonate,diethyl(2,2-dimethylpropylidene)malonate,dimethyl(2-methylbutylidene)malonate,diethyl(2-methylbutylidene)malonate,di-n-propyl(2-methylbutylidene)malonate,diisobutyl(2-methylbutylidene)malonate,di-n-butyl(2-methylbutylidene)malonate,dimethyl(2-ethylbutylidene)malonate, diethyl(2-ethylbutylidene)malonate,di-n-propyl(2-ethylbutylidene)malonate,diisobutyl(2-ethylbutylidene)malonate,di-n-butyl(2-ethylbutylidene)malonate,dimethyl(2-ethylpentylidene)malonate,diethyl(2-ethylpentylidene)malonate,di-n-propyl(2-ethylpentylidene)malonate,diisobutyl(2-ethylpentylidene)malonate,di-n-butyl(2-ethylpentylidene)malonate,dimethyl(2-isopropylbutylidene)malonate,diethyl(2-isopropylbutylidene)malonate,di-n-propyl(2-isopropylbutylidene)malonate,diisobutyl(2-isopropylbutylidene)malonate,di-n-butyl(2-isopropylbutylidene)malonate,dimethyl(3-methylbutylidene)malonate,diethyl(3-methylbutylidene)malonate,di-n-propyl(3-methylbutylidene)malonate,diisobutyl(3-methylbutylidene)malonate,di-n-butyl(3-methylbutylidene)malonate,dimethyl(2,3-dimethylbutylidene)malonate,diethyl(2,3-dimethylbutylidene)malonate,di-n-propyl(2,3-dimethylbutylidene)malonate,diisobutyl(2,3-dimethylbutylidene)malonate,di-n-butyl(2,3-dimethylbutyhdene)malonate,dimethyl(2-n-propylbutylidene)malonate,diethyl(2-n-propylbutylidene)malonate,di-n-propyl(2-n-propylbutylidene)malonate,diisobutyl(2-n-propylbutylidene)malonate,di-n-butyl(2-n-propylbutylidene)malonate,dimethyl(2-isobutyl-3-methylbutylidene)malonate,diethyl(2-isobutyl-3-methylbutylidene)malonate,di-n-propyl(2-isobutyl-3-methylbutylidene)malonate,diisobutyl(2-isobutyl-3-methylbutylidene)malonate,di-n-butyl(2-isobutyl-3-methylbutylidene)malonate,dimethyl(2-n-butylpentylidene)malonate,diethyl(2-n-butylpentylidene)malonate,di-n-propyl(2-n-butylpentylidene)malonate,diisobutyl(2-n-butylpentylidene)malonate,di-n-butyl(2-n-butylpentylidene)malonate,dimethyl(2-n-pentylhexylidene)malonate,diethyl(2-n-pentylhexylidene)malonate,di-n-propyl(2-n-pentylhexylidene)malonate,diisobutyl(2-n-pentylhexylidene)malonate,di-n-butyl(2-n-pentylhexylidene)malonate,dimethyl(cyclohexylmethylene)malonate,diethyl(cyclohexylmethylene)malonate,di-n-propyl(cyclohexylmethylene)malonate,diisobutyl(cyclohexylmethylene)malonate,di-n-butyl(cyclohexylmethylene)malonate,dimethyl(cyclopentylmethylene)malonate,diethyl(cyclopentylmethylene)malonate,di-n-propyl(cyclopentylmethylene)malonate,diisobutyl(cyclopentylmethylene)malonate,di-n-butyl(cyclopentylmethylene)malonate,dimethyl(1-methylpropylidene)malonate,diethyl(1-methylpropylidene)malonate,di-n-propyl(1-methylpropylidene)malonate,diisobutyl(1-methylpropylidene)malonate,di-n-butyl(1-methylpropylidene)malonate,diethyl(1-ethylpropylidene)malonate,dimethyl(di-t-butylmethylene)malonate,diethyl(di-t-butylmethylene)malonate,di-n-propyl(di-t-butylmethylene)malonate,diisobutyl(di-t-butylmethylene)malonate,di-n-butyl(di-t-butylmethylene)malonate,dimethyl(diisobutylmethylene)malonate,diethyl(diisobutylmethylene)malonate,di-n-propyl(diisobutylmethylene)malonate,diisobutyl(diisobutylmethylene)malonate,di-n-butyl(diisobutylmethylene)malonate,dimethyl(diisopropylmethylene)malonate,diethyl(diisopropylmethylene)malonate,di-n-propyl(diisopropylmethylene)malonate,diisobutyl(diisopropylmethylene)malonate,di-n-butyl(diisopropylmethylene)malonate,dimethyl(dicyclopentylmethylene)malonate,diethyl(dicyclopentylmethylene)malonate,di-n-propyl(dicyclopentylmethylene)malonate,diisobutyl(dicyclopentylmethylene)malonate,di-n-butyl(dicyclopentylmethylene)malonate,dimethyl(dicyclohexylmethylene)malonate,diethyl(dicyclohexylmethylene)malonate,di-n-propyl(dicyclohexylmethylene)malonate,diisobutyl(dicyclohexylmethylene)malonate,di-n-butyl(dicyclohexylmethylene)malonate, dimethyl benzylidenemalonate,diethyl benzylidenemalonate, di-n-propyl benzylidenemalonate, diisobutylbenzylidenemalonate, di-n-butyl benzylidenemalonate,dimethyl(1-methylbenzylidene)malonate,diethyl(1-methylbenzylidene)malonate,di-n-propyl(1-methylbenzylidene)malonate,diisobutyl(1-methylbenzylidene)malonate,di-n-butyl(1-methylbenzylidene)malonate,dimethyl(1-ethylbenzylidene)malonate,diethyl(1-ethylbenzylidene)malonate,di-n-propyl(1-ethylbenzylidene)malonate,diisobutyl(1-ethylbenzylidene)malonate,di-n-butyl(1-ethylbenzylidene)malonate,dimethyl(1-n-propylbenzylidene)malonate,diethyl(1-n-propylbenzylidene)malonate,di-n-propyl(1-n-propylbenzylidene)malonate,diisobutyl(1-n-propylbenzylidene)malonate,di-n-butyl(1-n-propylbenzylidene)malonate,dimethyl(1-isopropylbenzylidene)malonate,diethyl(1-isopropylbenzylidene)malonate,di-n-propyl(1-isopropylbenzylidene)malonate,diisobutyl(1-isopropylbenzylidene)malonate,di-n-butyl(1-isopropylbenzylidene)malonate,dimethyl(1-n-butylbenzylidene)malonate,diethyl(1-n-butylbenzylidene)malonate,di-n-propyl(1-n-butylbenzylidene)malonate,diisobutyl(1-n-butylbenzylidene)malonate,di-n-butyl(1-n-butylbenzylidene)malonate,dimethyl(1-isobutylbenzylidene)malonate,diethyl(1-isobutylbenzylidene)malonate,di-n-propyl(1-isobutylbenzylidene)malonate,diisobutyl(1-isobutylbenzylidene)malonate,di-n-butyl(1-isobutylbenzylidene)malonate,dimethyl(1-t-butylbenzylidene)malonate,diethyl(1-t-butylbenzylidene)malonate,di-n-propyl(1-t-butylbenzylidene)malonate,diisobutyl(1-t-butylbenzylidene)malonate,di-n-butyl(1-t-butylbenzylidene)malonate,dimethyl(1-n-pentylbenzylidene)malonate,diethyl(1-n-pentylbenzylidene)malonate,di-n-propyl(1-n-pentylbenzylidene)malonate,diisobutyl(1-n-pentylbenzylidene)malonate,di-n-butyl(1-n-pentylbenzylidene)malonate,dimethyl(2-methylphenylmethylene)malonate,diethyl(2-methylphenylmethylene)malonate,di-n-propyl(2-methylphenylmethylene)malonate,diisobutyl(2-methylphenylmethylene)malonate,di-n-butyl(2-methylphenylmethylene)malonate,dimethyl(4-methylphenylmethylene)malonate,dimethyl(2,6-dimethylphenylmethylene)malonate,diethyl(2,6-dimethylphenylmethylene)malonate,di-n-propyl(2,6-dimethylphenylmethylene)malonate,diisobutyl(2,6-dimethylphenylmethylene)malonate,di-n-butyl(2,6-dimethylphenylmethylene)malonate,dimethyl(1-methyl-1-(2-methylphenyl)methylene)malonate,diethyl(1-methyl-1-(2-methylphenyl)methylene)malonate,di-n-propyl(1-methyl-1-(2-methylphenyl)methylene)malonate,diisobutyl(1-methyl-1-(2-methylphenyl)methylene)malonate,di-n-butyl(1-methyl-1-(2-methylphenyl)methylene)malonate,dimethyl(2-methylcyclohexylmethylene)malonate,diethyl(2-methylcyclohexylmethylene)malonate,di-n-propyl(2-methylcyclohexylmethylene)malonate,diisobutyl(2-methylcyclohexylmethylene)malonate,di-n-butyl(2-methylcyclohexylmethylene)malonate,dimethyl(2,6-dimethylcyclohexylmethylene)malonate,diethyl(2,6-dimethylcyclohexylmethylene)malonate,di-n-propyl(2,6-dimethylcyclohexylmethylene)malonate,diisobutyl(2,6-dimethylcyclohexylmethylene)malonate,di-n-butyl(2,6-dimethylcyclohexylmethylene)malonate,dimethyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,diethyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,di-n-propyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,diisobutyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,di-n-butyl(1-methyl-1-(2-methylcyclohexyl)methylene)malonate,dimethyl(naphthylmethylene)malonate, diethyl(naphthylmethylene)malonate,di-n-propyl(naphthylmethylene)malonate,diisobutyl(naphthylmethylene)malonate,di-n-butyl(naphthylmethylene)malonate,dimethyl(1-n-hexylbenzylidene)malonate,diethyl(1-n-hexylbenzylidene)malonate,di-n-propyl(1-n-hexylbenzylidene)malonate,diisobutyl(1-n-hexylbenzylidene)malonate, anddi-n-butyl(1-n-hexylbenzylidene)malonate.

Among these, dialkylmalonic acid diesters and alkylidenemalonic aciddiesters are preferable, and dialkylmalonic acid diesters such asdimethyl ethylcyclopentylmalonate, diethyl ethylcyclopentylmalonate,dimethyl diisobutylmalonate, and diethyl diisobutylmalonate, andalkylidenemalonic acid diesters such as dimethyl benzylidenemalonate anddiethyl benzylidenemalonate are more preferable.

Examples of the alicyclic polycarboxylic acid ester include a saturatedalicyclic polycarboxylic acid ester and an unsaturated alicyclicpolycarboxylic acid ester. Specific examples of the alicyclicpolycarboxylic acid ester include a cycloalkanedicarboxylic aciddiester, a cycloalkenedicarboxylic acid diester, and the like.

Examples of the cycloalkanedicarboxylic acid diester that may be used asthe first internal electron donor compound include acyclopentane-1,2-dicarboxylic acid diester, acyclopentane-1,3-dicarboxylic acid diester, acyclohexane-1,2-dicarboxylic acid diester, acyclohexane-1,3-dicarboxylic acid diester, acycloheptane-1,2-dicarboxylic acid diester, acycloheptane-1,2-dicarboxylic acid diester, acyclooctane-1,2-dicarboxylic acid diester, acyclooctane-1,3-dicarboxylic acid diester, acyclononane-1,2-dicarboxylic acid diester, acyclononane-1,3-dicarboxylic acid diester, acyclodecane-1,2-dicarboxylic acid diester, acyclodecane-1,3-dicarboxylic acid diester, and the like.

Among these, compounds having a cycloalkane-1,2-dicarboxylic aciddiester structure, such as diethyl cyclopentane-1,2-dicarboxylate,diisopropyl cyclopentane-1,2-dicarboxylate, diisobutylcyclopentane-1,2-dicarboxylate, diheptyl cyclopentane-1,2-dicarboxylate,didecyl cyclopentane-1,2-dicarboxylate, di-n-butylcyclopentane-1,2-dicarboxylate, diethyl cyclohexane-1,2-dicarboxylate,di-n-propyl cyclohexane-1,2-dicarboxylate, diisopropylcyclohexane-1,2-dicarboxylate, di-n-butyl cyclohexane-1,2-dicarboxylate,diisobutyl cyclohexane-1,2-dicarboxylate, dihexylcyclohexane-1,2-dicarboxylate, diheptyl cyclohexane-1,2-dicarboxylate,dioctyl cyclohexane-1,2-dicarboxylate, di-2-ethylhexylcyclohexane-1,2-dicarboxylate, didecyl cyclohexane-1,2-dicarboxylate,diethyl cycloheptane-1,2-dicarboxylate, diisopropylcycloheptane-1,2-dicarboxylate, diisobutylcycloheptane-1,2-dicarboxylate, diheptyl cycloheptane-1,2-dicarboxylate,diethyl cyclooctane-1,2-dicarboxylate, and diethylcyclodecane-1,2-dicarboxylate, are preferable.

Examples of a substituted cycloalkanedicarboxylic acid diester (in whichsome of the hydrogen atoms of the cycloalkyl group are substituted withan alkyl group or the like) that may be used as the first internalelectron donor compound include diethyl3-methylcyclohexane-1,2-dicarboxylate, diethyl4-methylcyclohexane-1,2-dicarboxylate, diethyl5-methylcyclohexane-1,2-dicarboxylate, diethyl3,6-dimethylcyclohexane-1,2-dicarboxylate, di-n-butyl3,6-dimethylcyclohexane-1,2-dicarboxylate, and the like.

Examples of the cycloalkenedicarboxylic acid diester that may be used asthe first internal electron donor compound include acyclopentenedicarboxylic acid diester, a cyclohexenedicarboxylic aciddiester, a cycloheptenedicarboxylic acid diester, acyclooctenedicarboxylic acid diester, a cyclodecenedicarboxylic aciddiester, a biphenyldicarboxylic acid diester, and the like. Specificexamples of the cycloalkenedicarboxylic acid diester include1-cyclohexene-1,2-dicarboxylic acid diesters such as dimethyl1-cyclohexene-1,2-dicarboxylate, diethyl1-cyclohexene-1,2-dicarboxylate, di-n-propyl1-cyclohexene-1,2-dicarboxylate, diisopropyl1-cyclohexene-1,2-dicarboxylate, di-n-butyl1-cyclohexene-1,2-dicarboxylate, diisobutyl1-cyclohexene-1,2-dicarboxylate, dihexyl1-cyclohexene-1,2-dicarboxylate, diheptyl1-cyclohexene-1,2-dicarboxylate, dioctyl1-cyclohexene-1,2-dicarboxylate, didecyl1-cyclohexene-1,2-dicarboxylate, diethyl1-cyclohexene-1,3-dicarboxylate, and diisobutyl1-cyclohexene-1,3-dicarboxylate, 4-cyclohexene-1,2-dicarboxylic aciddiesters such as dimethyl 4-cyclohexene-1,2-dicarboxylate, diethyl4-cyclohexene-1,2-dicarboxylate, di-n-propyl4-cyclohexene-1,2-dicarboxylate, diisopropyl4-cyclohexene-1,2-dicarboxylate, di-n-butyl4-cyclohexene-1,2-dicarboxylate, diisobutyl4-cyclohexene-1,2-dicarboxylate, dihexyl4-cyclohexene-1,2-dicarboxylate, diheptyl4-cyclohexene-1,2-dicarboxylate, dioctyl4-cyclohexene-1,2-dicarboxylate, didecyl4-cyclohexene-1,2-dicarboxylate, diethyl4-cyclohexene-1,3-dicarboxylate, and diisobutyl4-cyclohexene-1,3-dicarboxylate, 3-cyclopentene-1,2-dicarboxylic aciddiesters such as diethyl 3-cyclopentene-1,2-dicarboxylate, diisopropyl3-cyclopentene-1,2-dicarboxylate, diisobutyl3-cyclopentene-1,2-dicarboxylate, and diheptyl3-cyclopentene-1,2-dicarboxylate, 3-cyclopentene-1,3-dicarboxylic aciddiesters such as didecyl 3-cyclopentene-1,2-dicarboxylate, diethyl3-cyclopentene-1,3-dicarboxylate, and diisobutyl3-cyclopentene-1,3-dicarboxylate, 4-cycloheptene-1,2-dicarboxylic aciddiesters such as diethyl 4-cycloheptene-1,2-dicarboxylate, diisopropyl4-cycloheptene-1,2-dicarboxylate, diisobutyl4-cycloheptene-1,2-dicarboxylate, diheptyl4-cycloheptene-1,2-dicarboxylate, and didecyl4-cycloheptene-1,2-dicarboxylate, diethyl4-cycloheptene-1,3-dicarboxylate, diisobutyl4-cycloheptene-1,3-dicarboxylate, diethyl5-cyclooctene-1,2-dicarboxylate, diethyl6-cyclodecene-1,2-dicarboxylate, and the like. It is preferable to useone compound, or two or more compounds, selected from1-cyclohexene-1,2-dicarboxylic acid diesters and4-cyclohexene-1,2-dicarboxylic acid diesters.

Examples of the diether that may be used as the first internal electrondonor compound include a compound represented by the following generalformula (VI).

R¹¹ _(k)H_((3-k))C—O—(CR₁₂R₁₃)_(m)—O—CR¹⁴ _(n)H_((3-n))  (VI)

wherein R¹¹ and R¹⁴ are a halogen atom or an organic group having 1 to20 carbon atoms, provided that R¹¹ and R¹⁴ are either identical ordifferent, and R¹² and R¹³ are a hydrogen atom, an oxygen atom, a sulfuratom, a halogen atom, or an organic group having 1 to 20 carbon atoms,provided that R¹² and R¹³ are either identical or different. The organicgroup having 1 to 20 carbon atoms may include at least one atom selectedfrom an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom,an iodine atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and aboron atom. When a plurality of organic groups having 1 to 20 carbonatoms are present, the plurality of organic groups may bond to eachother to form a ring. k is an integer from 0 to 3. When k is an integerequal to or larger than 2, a plurality of R¹¹ are either identical ordifferent. m is an integer from 1 to 10. When m is an integer equal toor larger than 2, a plurality of R¹² are either identical or different,and a plurality of R¹³ are either identical or different. n is aninteger from 0 to 3. When n is an integer equal to or larger than 2, aplurality of R¹⁴ are either identical or different.

When R¹¹ or R¹⁴ in the compound represented by the general formula (VI)is a halogen atom, the halogen atom may be a fluorine atom, a chlorineatom, a bromine atom, or an iodine atom. The halogen atom is preferablya fluorine atom, a chlorine atom, or a bromine atom.

Examples of the organic group having 1 to 20 carbon atoms represented byR¹¹ or R¹⁴ include a methyl group, an ethyl group, an isopropyl group,an isobutyl group, a n-propyl group, a n-butyl group, a t-butyl group, ahexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group,and a phenyl group. Among these, a methyl group and an ethyl group arepreferable.

When the compound represented by the general formula (VI) includes aplurality of organic groups having 1 to 20 carbon atoms, the pluralityof organic groups may bond to each other to form a ring. In this case,(1) R¹¹ and R¹¹ (when k is equal to or larger than 2), (2) R¹⁴ and R¹⁴(when n is equal to or larger than 2), (3) R¹² and R¹² (when m is equalto or larger than 2), (4) R¹³ and R¹³ (when m is equal to or larger than2), (5) R¹¹ and R¹², (6) R¹¹ and R¹³, (7) R¹¹ and R¹⁴, (8) R¹² and R¹³,(9) R¹² and R¹⁴, or (10) R¹³ and R¹⁴ may bond to each other to form aring. It is preferable that R¹² and R¹³ (see (8)) bond to each other toform a ring. It is more preferable that R¹² and R¹³ bond to each otherto form a fluorene ring or the like.

Specific examples of the compound represented by the general formula(VI) include 2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane,2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,9,9-bis(methoxymethyl)fluorene, 9,9-bis(ethoxymethyl)fluorene,9-methoxy-9-ethoxymethylfluorene,9,9-bis(methoxymethyl)-2,7-dimethylfluorene,9,9-bis(methoxymethyl)-2,6-diisopropylfluorene,9,9-bis(methoxymethyl)-3,6-diisobutylfluorene,9,9-bis(methoxymethyl)-2-isobutyl-7-isopropylfluorene,9,9-bis(methoxymethyl)-2,7-dichlorofluorene,9,9-bis(methoxymethyl)-2-chloro-7-isopropylfluorene, and the like. Amongthese, 2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,3,3-bis(methoxymethyl)-2,6-dimethylheptane,9,9-bis(methoxymethyl)fluorene, and the like are preferable, and onecompound, or two or more compounds, selected from2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,3,3-bis(methoxymethyl)-2,6-dimethylheptane, and9,9-bis(methoxymethyl)fluorene are more preferable. The compoundrepresented by the general formula (VI) is particularly preferably2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane, or9,9-bis(methoxymethyl)fluorene.

k in the compound represented by the general formula (VI) is an integerfrom 0 to 3, preferably an integer from 0 to 2, and more preferably 0or 1. When k is an integer equal to or larger than 2, a plurality of R¹¹are either identical or different.

m in the compound represented by the general formula (VI) is an integerfrom 1 to 10, preferably an integer from 1 to 8, and more preferably aninteger from 1 to 6. When m is an integer equal to or larger than 2, aplurality of R¹² are either identical or different, and a plurality ofR¹³ are either identical or different.

n in the compound represented by the general formula (VI) is an integerfrom 0 to 3, preferably an integer from 0 to 2, and more preferably 0or 1. When n is an integer equal to or larger than 2, a plurality of R¹⁴are either identical or different.

Examples of the ether carbonate that may be used as the first internalelectron donor compound include a compound represented by the followinggeneral formula (VII).

R¹⁵—O—C(═O)—O—Z—OR¹⁶  (VII)

wherein R¹⁵ and R¹⁶ are a linear alkyl group having 1 to 20 carbonatoms, a branched alkyl group having 3 to 20 carbon atoms, a vinylgroup, a linear or branched alkenyl group having 3 to 20 carbon atoms, alinear halogen-substituted alkyl group having 1 to 20 carbon atoms, abranched halogen-substituted alkyl group having 3 to 20 carbon atoms, alinear halogen-substituted alkenyl group having 2 to 20 carbon atoms, abranched halogen-substituted alkenyl group having 3 to 20 carbon atoms,a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl grouphaving 3 to 20 carbon atoms, a halogen-substituted cycloalkyl grouphaving 3 to 20 carbon atoms, a halogen-substituted cycloalkenyl grouphaving 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to24 carbon atoms, a halogen-substituted aromatic hydrocarbon group having6 to 24 carbon atoms, a nitrogen atom-containing hydrocarbon grouphaving 2 to 24 carbon atoms that is terminated by a carbon atom(provided that a group that is terminated by a C═N group is excluded),an oxygen atom-containing hydrocarbon group having 2 to 24 carbon atomsthat is terminated by a carbon atom (provided that a group that isterminated by a carbonyl group is excluded), or a phosphorus-containinghydrocarbon group having 2 to 24 carbon atoms that is terminated by acarbon atom (provided that a group that is terminated by a C═P group isexcluded), provided that R¹⁵ and R¹⁶ are either identical or different,and Z is a linking group that bonds the oxygen atoms through a carbonatom or a carbon chain.

Examples of the linear alkyl group having 1 to 20 carbon atoms that maybe represented by R¹⁵ and R¹⁶ in the general formula (VII) include amethyl group, an ethyl group, a n-propyl group, a n-butyl group, an-pentyl group, a n-hexyl group, a n-pentyl group, a n-octyl group, an-nonyl group, a n-decyl group, and the like. Among these, linear alkylgroups having 1 to 12 carbon atoms are preferable.

Examples of the branched alkyl group having 3 to 20 carbon atoms thatmay be represented by R¹⁵ and R¹⁶ include alkyl groups that include asecondary carbon atom or a tertiary carbon atom (e.g., isopropyl group,isobutyl group, t-butyl group, isopentyl group, and neopentyl group).Among these, branched alkyl groups having 3 to 12 carbon atoms arepreferable.

Examples of the linear alkenyl group having 3 to 20 carbon atoms thatmay be represented by R¹⁵ and R¹⁶ include an allyl group, a 3-butenylgroup, a 4-hexenyl group, a 5-hexenyl group, a 7-octenyl group, a10-dodecenyl group, and the like. Among these, linear alkenyl groupshaving 3 to 12 carbon atoms are preferable.

Examples of the branched alkenyl group having 3 to 20 carbon atoms thatmay be represented by R¹⁵ and R¹⁶ include an isopropenyl group, anisobutenyl group, an isopentenyl group, a 2-ethyl-3-hexenyl group, andthe like. Among these, branched alkenyl groups having 3 to 12 carbonatoms are preferable.

Examples of the linear halogen-substituted alkyl group having 1 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include a methylhalide group, an ethyl halide group, a n-propyl halide group, a n-butylhalide group, a n-pentyl halide group, an n-hexyl halide group, an-pentyl halide group, an n-octyl halide group, a nonyl halide group, adecyl halide group, a halogen-substituted undecyl group, ahalogen-substituted dodecyl group, and the like. Among these, linearhalogen-substituted alkyl groups having 1 to 12 carbon atoms arepreferable.

Examples of the branched halogen-substituted alkyl group having 3 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include an isopropylhalide group, an isobutyl halide group, a 2-ethylhexyl halide group, aneopentyl halide group, and the like. Among these, branchedhalogen-substituted alkyl groups having 3 to 12 carbon atoms arepreferable.

Examples of the linear halogen-substituted alkenyl group having 2 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include a2-halogenated vinyl group, a 3-halogenated allyl group, a 3-halogenated2-butenyl group, a 4-halogenated 3-butenyl group, a perhalogenated2-butenyl group, a 6-halogenated 4-hexenyl group, a 3-trihalogenatedmethyl-2-propenyl group, and the like. Among these, linearhalogen-substituted alkenyl groups having 2 to 12 carbon atoms arepreferable.

Examples of the branched halogen-substituted alkenyl group having 3 to20 carbon atoms that may be represented by R¹⁵ and R¹⁶ include a3-trihalogenated 2-butenyl group, a 2-pentahalogenated ethyl-3-hexenylgroup, a 6-halogenated 3-ethyl-4-hexenyl group, a 3-halogenatedisobutenyl group, and the like. Among these, branchedhalogen-substituted alkenyl groups having 3 to 12 carbon atoms arepreferable.

Examples of the cycloalkyl group having 3 to 20 carbon atoms that may berepresented by R¹⁵ and R¹⁶ include a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a tetramethylcyclopentyl group, a cyclohexylgroup, a methylcyclohexyl group, a cycloheptyl group, a cyclooctylgroup, a cyclononyl group, a cyclodecyl group, a butylcyclopentyl group,and the like. Among these, cycloalkyl groups having 3 to 12 carbon atomsare preferable.

Examples of the cycloalkenyl group having 3 to 20 carbon atoms that maybe represented by R¹⁵ and R¹⁶ include a cyclopropenyl group, acyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, anorbornene group, and the like. Among these, cycloalkenyl groups having3 to 12 carbon atoms are preferable.

Examples of the halogen-substituted cycloalkyl group having 3 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include ahalogen-substituted cyclopropyl group, a halogen-substituted cyclobutylgroup, a halogen-substituted cyclopentyl group, a halogen-substitutedtrimethylcyclopentyl group, a halogen-substituted cyclohexyl group, ahalogen-substituted methylcyclohexyl group, a halogen-substitutedcycloheptyl group, a halogen-substituted cyclooctyl group, ahalogen-substituted cyclononyl group, a halogen-substituted cyclodecylgroup, a halogen-substituted butylcyclopentyl group, and the like. Amongthese, halogen-substituted cycloalkyl groups having 3 to 12 carbon atomsare preferable.

Examples of the halogen-substituted cycloalkenyl group having 3 to 20carbon atoms that may be represented by R¹⁵ and R¹⁶ include ahalogen-substituted cyclopropenyl group, a halogen-substitutedcyclobutenyl group, a halogen-substituted cyclopentenyl group, ahalogen-substituted trimethylcyclopentenyl group, a halogen-substitutedcyclohexenyl group, a halogen-substituted methylcyclohexenyl group, ahalogen-substituted cycloheptenyl group, a halogen-substitutedcyclooctenyl group, and halogen-substituted cyclononenyl group, ahalogen-substituted cyclodecenyl group, a halogen-substitutedbutylcyclopentenyl group, and the like. Among these, halogen-substitutedcycloalkenyl groups having 3 to 12 carbon atoms are preferable.

Examples of the aromatic hydrocarbon group having 6 to 24 carbon atomsthat may be represented by R¹⁵ and R¹⁶ include a phenyl group, amethylphenyl group, a dimethylphenyl group, an ethylphenyl group, abenzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a2-phenylpropyl group, a 1-phenylbutyl group, a 4-phenylbutyl group, a2-phenylheptyl group, a tolyl group, a xylyl group, a naphthyl group, a1,8-dimethylnaphthyl group, and the like. Among these, aromatichydrocarbon groups having 6 to 12 carbon atoms are preferable.

Examples of the halogen-substituted aromatic hydrocarbon group having 6to 24 carbon atoms that may be represented by R¹⁵ and R¹⁶ include aphenyl halide group, a methylphenyl halide group, a methylphenyltrihalide group, a benzyl perhalide group, a phenyl perhalide group, a2-phenyl-2-halogenated ethyl group, a naphthyl perhalide group, a4-phenyl-2,3-dihalogenated butyl group, and the like. Among these,halogen-substituted aromatic hydrocarbon groups having 6 to 12 carbonatoms are preferable.

When R¹⁵ or R¹⁶ in the compound represented by the general formula (VII)is a group that includes a halogen atom, the halogen atom may be afluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Thehalogen atom is preferably a fluorine atom, a chlorine atom, or abromine atom.

Examples of the phosphorus-containing hydrocarbon group having 2 to 24carbon atoms terminated by a carbon atom (provided that a group that isterminated by a C═P group is excluded) that may be represented by R¹⁵and R¹⁶ include dialkylphosphinoalkyl groups such as adimethylphosphinomethyl group, a dibutylphosphinomethyl group, adicyclohexylphosphinomethyl group, a dimethylphosphinoethyl group, adibutylphosphinoethyl group, and a dicyclohexylphosphinoethyl group,diarylphosphinoalkyl groups such as a diphenylphosphinomethyl group anda ditolylphosphinomethyl group, phosphino group-substituted aryl groupssuch as a dimethylphosphinophenyl group and a diethylphosphinophenylgroup, and the like. Among these, phosphorus-containing hydrocarbongroups having 2 to 12 carbon atoms are preferable.

Note that the expression “terminated by” used herein in connection withR¹⁵ and R¹⁶ means that R¹⁵ or R¹⁶ is bonded to the adjacent oxygen atomthrough an atom or a group by which R¹⁵ or R¹⁶ is terminated.

R¹⁵ is preferably a linear alkyl group having 1 to 12 carbon atoms, abranched alkyl group having 3 to 12 carbon atoms, a vinyl group, alinear or branched alkenyl group having 3 to 12 carbon atoms, a linearhalogen-substituted alkyl group having 1 to 12 carbon atoms, a branchedhalogen-substituted alkyl group having 3 to 12 carbon atoms, a linear orbranched halogen-substituted alkenyl group having 3 to 12 carbon atoms,a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl grouphaving 3 to 12 carbon atoms, a halogen-substituted cycloalkyl grouphaving 3 to 12 carbon atoms, a halogen-substituted cycloalkenyl grouphaving 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6to 12 carbon atoms, more preferably a linear alkyl group having 1 to 12carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, avinyl group, a linear or branched alkenyl group having 3 to 12 carbonatoms, a linear halogen-substituted alkyl group having 1 to 12 carbonatoms, a branched halogen-substituted alkyl group having 3 to 12 carbonatoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenylgroup having 3 to 12 carbon atoms, or an aromatic hydrocarbon grouphaving 6 to 12 carbon atoms, and still more preferably a linear alkylgroup having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbonatoms.

R¹⁶ is preferably a linear alkyl group having 1 to 12 carbon atoms, abranched alkyl group having 3 to 12 carbon atoms that is terminated by—CH₂—, a vinyl group, a linear alkenyl group having 3 to 12 carbonatoms, a branched alkenyl group having 3 to 12 carbon atoms that isterminated by —CH₂—, a linear halogen-substituted alkyl group having 1to 12 carbon atoms, a branched halogen-substituted alkyl group having 3to 12 carbon atoms that is terminated by —CH₂—, a linearhalogen-substituted alkenyl group having 3 to 12 carbon atoms, abranched halogen-substituted alkenyl group having 3 to 12 carbon atomsthat is terminated by —CH₂—, a cycloalkyl group having 4 to 12 carbonatoms that is terminated by —CH₂—, a cycloalkenyl group having 4 to 12carbon atoms that is terminated by —CH₂—, a halogen-substitutedcycloalkyl group having 4 to 12 carbon atoms that is terminated by—CH₂—, a halogen-substituted cycloalkenyl group having 4 to 12 carbonatoms that is terminated by —CH₂—, or an aromatic hydrocarbon grouphaving 7 to 12 carbon atoms that is terminated by —CH₂—, more preferablya linear alkyl group having 1 to 12 carbon atoms, a branched alkyl grouphaving 3 to 12 carbon atoms that is terminated by —CH₂—, a branchedalkenyl group having 3 to 12 carbon atoms that is terminated by —CH₂—, alinear halogen-substituted alkyl group having 1 to 12 carbon atoms thatis terminated by —CH₂—, a branched halogen-substituted alkyl grouphaving 3 to 12 carbon atoms that is terminated by —CH₂—, a branchedhalogen-substituted alkenyl group having 3 to 12 carbon atoms that isterminated by —CH₂—, a cycloalkyl group having 4 to 12 carbon atoms thatis terminated by —CH₂—, a cycloalkenyl group having 4 to 12 carbon atomsthat is terminated by —CH₂—, a halogen-substituted cycloalkyl grouphaving 4 to 12 carbon atoms that is terminated by —CH₂—, ahalogen-substituted cycloalkenyl group having 4 to 12 carbon atoms thatis terminated by —CH₂—, or an aromatic hydrocarbon group having 7 to 12carbon atoms that is terminated by —CH₂—, and still more preferably alinear hydrocarbon group having 1 to 12 carbon atoms, a branched alkylgroup having 3 to 12 carbon atoms that is terminated by —CH₂—, or anaromatic hydrocarbon group having 7 to 12 carbon atoms that isterminated by —CH₂—.

Note that the expression “terminated by” used herein in connection withR¹⁶ means that R¹⁶ is bonded to the adjacent oxygen atom included in thecompound represented by the general formula (VII) through an atom or agroup by which R¹⁶ is terminated.

Examples of a combination of R⁵ and R¹⁶ include combinations of groupsmentioned above as preferable groups. It is preferable that R¹⁵ and R¹⁶be a combination of groups mentioned above as more preferable groups.

Z in the compound represented by the general formula (VII) is a divalentlinking group that bonds the carbonate group and the ether group (OR¹⁶)through a carbon atom or a carbon chain. Z may be a linking group thatbonds the two oxygen atoms bonded to Z (i.e., bonded through Z) througha carbon chain, for example. It is preferable that Z be a linking groupin which the carbon chain includes two carbon atoms.

Z is preferably a linear alkylene group having 1 to 20 carbon atoms, abranched alkylene group having 3 to 20 carbon atoms, a vinylene group, alinear or branched alkenylene group having 3 to 20 carbon atoms, alinear halogen-substituted alkylene group having 1 to 20 carbon atoms, abranched halogen-substituted alkylene group having 3 to 20 carbon atoms,a linear or branched halogen-substituted alkenylene group having 3 to 20carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, acycloalkenylene group having 3 to 20 carbon atoms, a halogen-substitutedcycloalkylene group having 3 to 20 carbon atoms, a halogen-substitutedcycloalkenylene group having 3 to 20 carbon atoms, an aromatichydrocarbon group having 6 to 24 carbon atoms, a halogen-substitutedaromatic hydrocarbon group having 6 to 24 carbon atoms, a nitrogenatom-containing hydrocarbon group having 1 to 24 carbon atoms, an oxygenatom-containing hydrocarbon group having 1 to 24 carbon atoms, or aphosphorus-containing hydrocarbon group having 1 to 24 carbon atoms.

Z is more preferably an ethylene group having 2 carbon atoms, a branchedalkylene group having 3 to 12 carbon atoms, a vinylene group, a linearor branched alkenylene group having 3 to 12 carbon atoms, a linearhalogen-substituted alkylene group having 2 to 12 carbon atoms, abranched halogen-substituted alkylene group having 3 to 12 carbon atoms,a linear or branched halogen-substituted alkenylene group having 3 to 12carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, acycloalkenylene group having 3 to 12 carbon atoms, a halogen-substitutedcycloalkylene group having 3 to 12 carbon atoms, a halogen-substitutedcycloalkenylene group having 3 to 12 carbon atoms, an aromatichydrocarbon group having 6 to 12 carbon atoms, a halogen-substitutedaromatic hydrocarbon group having 6 to 12 carbon atoms, a nitrogenatom-containing hydrocarbon group having 2 to 12 carbon atoms, an oxygenatom-containing hydrocarbon group having 2 to 12 carbon atoms, or aphosphorus-containing hydrocarbon group having 2 to 12 carbon atoms, andstill more preferably a bidentate linking group selected from anethylene group having 2 carbon atoms and a branched alkylene grouphaving 3 to 12 carbon atoms. Note that the term “bidentate linkinggroup” used herein refers to a group in which two oxygen atoms bonded toZ are bonded through a carbon chain, and the carbon chain includes twocarbon atoms.

Examples of the linear alkylene group having 1 to 20 carbon atoms thatmay be represented by Z include an ethylene group, a trimethylene group,a tetramethylene group, a pentamethylene group, a hexamethylene group, aheptamethylene group, an octamethylene group, a nonamethylene group, adecamethylene group, an undecamethylene group, a dodecamethylene group,a tridecamethylene group, a tetradecamethylene group, and the like.Among these, linear alkylene groups having 2 to 12 carbon atoms arepreferable, and an ethylene group is more preferable.

Examples of the branched alkylene group having 3 to 20 carbon atoms thatmay be represented by Z include a 1-methylethylene group, a2-methyltrimethylene group, a 2-methyltetramethylene group, a2-methylpentamethylene group, a 3-methylhexamethylene group, a4-methylheptamethylene group, a 4-methyloctamethylene group, a5-methylnonamethylene group, a 5-methyldecamethylene group, a6-methylundecamethylene group, a 7-methyldodecamethylene group, a7-methyltridecamethylene group, and the like. Among these, branchedalkylene groups having 3 to 12 carbon atoms are preferable, and a1-methylethylene group, a 2-methylethylene group, and a 1-ethylethylenegroup are more preferable.

Examples of the linear alkenylene group having 3 to 20 carbon atoms thatmay be represented by Z include a propenylene group, a butenylene group,a hexenylene group, an octenylene group, an octadecenylene group, andthe like. Among these, linear alkenylene groups having 3 to 12 carbonatoms are preferable.

Examples of the branched alkenylene group having 3 to 20 carbon atomsthat may be represented by Z include an isopropenylene group, a1-ethylethenylene group, a 2-methylpropenylene group, a2,2-dimethylbutenylene group, a 3-methyl-2-butenylene group, a3-ethyl-2-butenylene group, a 2-methyloctenylene group, a2,4-dimethyl-2-butenylene group, and the like. Among these, branchedalkenylene groups having 3 to 12 carbon atoms that includes anethenylene linking group are preferable, and an isopropenylene group anda 1-ethylethenylene group are more preferable.

Examples of the linear halogen-substituted alkylene group having 1 to 20carbon atoms that may be represented by Z include a dichloromethylenegroup, a chloromethylene group, a dichloromethylene group, atetrachloroethylene group, and the like. Among these, linearhalogen-substituted alkylene groups having 3 to 12 carbon atoms arepreferable, and a chloroethylene group, a fluoroethylene group, adichloroethylene group, a difluoroethylene group, and atetrafluoroethylene group are more preferable.

Examples of the branched halogen-substituted alkylene group having 1 to20 carbon atoms that may be represented by Z include a1,2-bischloromethylethylene group, a 2,2-bis(chloromethyl)propylenegroup, a 1,2-bisdichloromethylethylene group, a1,2-bis(trichloromethyl)ethylene group, a 2,2-dichloropropylene group, a1,1,2,2-tetrachloroethylene group, a 1-trifluoromethylethylene group, a1-pentafluorophenylethylene group, and the like. Among these, branchedhalogen-substituted alkylene groups having 3 to 12 carbon atoms arepreferable, and a 1-chloroethylethylene group, a1-trifluoromethylethylene group, and a 1,2-bis(chloromethyl)ethylenegroup are more preferable.

Examples of the linear halogen-substituted alkenylene group having 1 to20 carbon atoms that may be represented by Z include adichloroethenylene group, a difluoroethenylene group, a3,3-dichloropropenylene group, a 1,2-difluoropropenylene group, and thelike. Among these, linear halogen-substituted alkenylene groups having 3to 12 carbon atoms are preferable, and a dichloroethenylene group and adifluoroethenylene group are more preferable.

Examples of the branched halogen-substituted alkylene group having 1 to20 carbon atoms that may be represented by Z include a3,4-dichloro-1,2-butylene group, a 2,2-dichloro-1,3-butylene group, a1,2-difluoro-1,2-propylene group, and the like. Among these, branchedhalogen-substituted alkylene groups having 3 to 12 carbon atoms arepreferable, and a chloromethylethenylene group, atrifluoromethylethenylene group, a 3,4-dichloro-1,2-butenylene group aremore preferable.

Examples of the cycloalkylene group having 3 to 20 carbon atoms that maybe represented by Z include a cyclopentylene group, a cyclohexylenegroup, a cyclopropylene group, a 2-methylcyclopropylene group, acyclobutylene group, a 2,2-dimethylcyclobutylene group, a2,3-dimethylcyclopentylene group, a 1,3,3-trimethylcyclohexylene group,a cyclooctylene group, and the like. Among these, cycloalkylene groupshaving 3 to 12 carbon atoms are preferable, and a 1,2-cycloalkylenegroup and a hydrocarbon group-substituted 1,2-cycloalkylene group aremore preferable.

Examples of the cycloalkenylene group having 3 to 20 carbon atoms thatmay be represented by Z include a cyclopentenylene group, a2,4-cyclopentadienylene group, a cyclohexenylene group, a1,4-cyclohexadienyl group, a cycloheptenylene group, amethylcyclopentenylene group, a methylcyclohexenylene group, amethylcycloheptenylene group, a dicyclodecylene group, atricyclodecylene group, and the like. Among these, cycloalkenylenegroups having 3 to 12 carbon atoms are preferable, and a1,2-cycloalkenylene group and a hydrocarbon group-substituted1,2-cycloalkenylene group are more preferable.

Examples of the halogen-substituted cycloalkylene group having 3 to 20carbon atoms that may be represented by Z include a3-chloro-1,2-cyclopentylene group, a3,4,5,6-tetrachloro-1,2-cyclohexylene group, a3,3-dichloro-1,2-cyclopropylene group, a 2-chloromethylcyclopropylenegroup, a 3,4-dichloro-1,2-cyclobutylene group, a3,3-bis(dichloromethyl)-1,2-cyclobutylene group, a2,3-bis(dichloromethyl)cyclopentylene group, a1,3,3-tris(fluoromethyl)-1,2-cyclohexylene group, a3-trichloromethyl-1,2-cyclooctylene group, and the like. Among these,halogen-substituted cycloalkylene groups having 3 to 12 carbon atoms arepreferable.

Examples of the halogen-substituted cycloalkenylene group having 3 to 20carbon atoms that may be represented by Z include a5-chloro-1,2-cyclo-4-hexenylene group, a3,3,4,4-tetrafluoro-1,2-cyclo-6-octenylene group, and the like. Amongthese, halogen-substituted cycloalkenylene groups having 3 to 12 carbonatoms are preferable.

Examples of the aromatic hydrocarbon group having 6 to 24 carbon atomsthat may be represented by Z include a 1,2-phenylene group, a3-methyl-1,2-phenylene group, a 3,6-dimethyl-1,2-phenylene group, a1,2-naphthylene group, a 2,3-naphthylene group, a5-methyl-1,2-naphthylene group, a 9,10-phenanthrylene group, a1,2-anthracenylene group, and the like. Among these, aromatichydrocarbon groups having 6 to 12 carbon atoms are preferable.

Examples of the halogen-substituted aromatic hydrocarbon group having 6to 24 carbon atoms that may be represented by Z include a3-chloro-1,2-phenylene group, a 3-chloromethyl-1,2-phenylene group, a3,6-dichloro-1,2-phenylene group, a3,6-dichloro-4,5-dimethyl-1,2-phenylene group, a3-chloro-1,2-naphthylene group, a 3-fluoro-1,2-naphthylene group, a3,6-dichloro-1,2-phenylene group, a 3,6-difluoro-1,2-phenylene group, a3,6-dibromo-1,2-phenylene group, a 1-chloro-2,3-naphthylene group, a5-chloro-1,2-naphthylene group, a 2,6-dichloro-9,10-phenanthrylenegroup, a 5,6-dichloro-1,2-anthracenylene group, a5,6-difluoro-1,2-anthracenylene, and the like. Among these,halogen-substituted aromatic hydrocarbon groups having 6 to 12 carbonatoms are preferable.

Examples of the nitrogen atom-containing hydrocarbon group having 1 to24 carbon atoms that may be represented by Z include a1-dimethylaminoethylene group, a 1,2-bisdimethylaminoethylene group, a1-diethylaminoethylene group, a 2-diethylamino-1,3-propylene group, a2-ethylamino-1,3-propylene group, a 4-dimethylamino-1,2-phenylene group,a 4,5-bis(dimethylamino)phenylene group, and the like. Among these,nitrogen atom-containing hydrocarbon groups having 2 to 12 carbon atomsare preferable.

Examples of the oxygen atom-containing hydrocarbon group having 1 to 24carbon atoms that may be represented by Z include a 1-methoxyethylenegroup, a 2,2-dimethoxy-1,3-propanylene group, a 2-ethoxy-1,3-propanylenegroup, a 2-t-butoxy-1,3-propanylene group, a 2,3-dimethoxy-2,3-butylenegroup, a 4-methoxy-1,2-phenylene group, and the like. Among these,oxygen atom-containing hydrocarbon groups having 2 to 12 carbon atomsare preferable.

Examples of the phosphorus-containing hydrocarbon group having 1 to 24carbon atoms that may be represented by Z include a1-dimethylphosphinoethylene group, a2,2-bis(dimethylphosphino)-1,3-propanylene group, a2-diethylphosphino-1,3-propanylene group, a2-t-butoxymethylphosphino-1,3-propanylene group, a2,3-bis(diphenylphospino)-2,3-butylene group, a4-methylphosphate-1,2-phenylene group, and the like. Among these,phosphorus-containing hydrocarbon groups having 1 to 12 carbon atoms arepreferable.

When Z is a cyclic group (e.g., cycloalkylene group, cycloalkenylenegroup, halogen-substituted cycloalkylene group, halogen-substitutedcycloalkenylene group, aromatic hydrocarbon group, orhalogen-substituted aromatic hydrocarbon group), the two oxygen atomsbonded to Z may be bonded through two adjacent carbon atoms that formthe cyclic group.

Specific examples of the compound represented by the general formula(VII) include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methylcarbonate, 2-propoxyethyl methyl carbonate, 2-(2-ethoxyethyloxyl)ethylmethyl carbonate, 2-benzyloxyethyl methyl carbonate, 2-methoxypropylmethyl carbonate, 2-ethoxypropyl methyl carbonate,2-methyl(2-methoxy)butyl methyl carbonate, 2-methyl(2-ethoxy)butylmethyl carbonate, 2-methyl(2-methoxy)pentyl methyl carbonate,2-methyl(2-ethoxy)pentyl methyl carbonate, 1-phenyl(2-methoxy) propylcarbonate, 1-phenyl(2-ethoxy)propyl methyl carbonate,1-phenyl(2-benzyloxy)propyl methyl carbonate, 1-phenyl(2-methoxy)ethylmethyl carbonate, 1-phenyl(2-ethoxy)ethyl methyl carbonate,1-methyl-1-phenyl(2-methoxy)ethyl methyl carbonate,1-methyl-1-phenyl(2-ethoxy)ethyl methyl carbonate,1-methyl-1-phenyl(2-benzyloxy)ethyl methyl carbonate,1-methyl-1-phenyl(2-(2-ethoxyethyloxy))ethyl methyl carbonate,2-methoxyethyl ethyl carbonate, 2-ethoxyethyl ethyl carbonate,1-phenyl(2-methoxy)ethyl ethyl carbonate, 1-phenyl(2-ethoxy)ethyl ethylcarbonate, 1-phenyl(2-propoxy)ethyl ethyl carbonate,1-phenyl(2-butoxy)ethyl ethyl carbonate, 1-phenyl(2-isobutyloxy)ethylethyl carbonate, 1-phenyl(2-(2-ethoxyethyloxy))ethyl ethyl carbonate,1-methyl-1-phenyl(2-methoxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-ethoxy) ethyl ethyl carbonate,1-methyl-1-phenyl(2-propoxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-butoxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-isobutyloxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-benzyloxy)ethyl ethyl carbonate,1-methyl-1-phenyl(2-(2-ethoxyethyloxy))ethyl ethyl carbonate,2-methoxyethyl phenyl carbonate, 2-ethoxyethyl phenyl carbonate,2-propoxyethyl phenyl carbonate, 2-butoxyethyl phenyl carbonate,2-isobutyloxyethyl phenyl carbonate, 2-benzyloxyethyl phenyl carbonate,2-(2-ethoxyethyloxyl)ethyl phenyl carbonate, 2-methoxyethylp-methylphenyl carbonate, 2-ethoxyethyl p-methylphenyl carbonate,2-propoxyethyl p-methylphenyl carbonate, 2-butoxyethyl p-methylphenylcarbonate, 2-isobutyloxyethyl p-methylphenyl carbonate, 2-benzyloxyethylp-methylphenyl carbonate, 2-(2-ethoxyethyloxyl)ethyl p-methylphenylcarbonate, 2-methoxyethyl o-methylphenyl carbonate, 2-ethoxyethylo-methylphenyl carbonate, 2-propoxyethyl o-methylphenyl carbonate,2-butoxyethyl o-methylphenyl carbonate, 2-isobutyloxyethylo-methylphenyl carbonate, 2-benzyloxyethyl o-methylphenyl carbonate,2-(2-ethoxyethyloxyl)ethyl o-methylphenyl carbonate, 2-methoxyethylo,p-dimethylphenyl carbonate, 2-ethoxyethyl o,p-dimethylphenylcarbonate, 2-propoxyethyl o,p-dimethylphenyl carbonate, 2-butoxyethylo,p-dimethylphenyl carbonate, 2-isobutyloxyethyl o,p-dimethylphenylcarbonate, 2-benzyloxyethyl o,p-dimethylphenyl carbonate,2-(2-ethoxyethyloxyl)ethyl o,p-dimethylphenyl carbonate, 2-methoxypropylphenyl carbonate, 2-ethoxypropyl phenyl carbonate, 2-propoxypropylphenyl carbonate, 2-butoxypropyl phenyl carbonate, 2-isobutyloxypropylphenyl carbonate, 2-(2-ethoxyethyloxyl)propyl phenyl carbonate,2-phenyl(2-methoxy)ethyl phenyl carbonate, 2-phenyl(2-ethoxy)ethylphenyl carbonate, 2-phenyl(2-propoxy)ethyl phenyl carbonate,2-phenyl(2-butoxy)ethyl phenyl carbonate, 2-phenyl(2-isobutyloxy)ethylphenyl carbonate, 2-phenyl(2-(2-ethoxyethyloxy))ethyl phenyl carbonate,1-phenyl(2-methoxy)propyl phenyl carbonate, 1-phenyl(2-ethoxy)propylphenyl carbonate, 1-phenyl(2-propoxy)propyl phenyl carbonate,1-phenyl(2-isobutyloxy)propyl phenyl carbonate, 1-phenyl(2-methoxy)ethylphenyl carbonate, 1-phenyl(2-ethoxy)ethyl phenyl carbonate,1-phenyl(2-propoxy)ethyl phenyl carbonate, 1-phenyl(2-butoxy)ethylphenyl carbonate, 1-phenyl(2-isobutyloxy)ethyl phenyl carbonate,1-phenyl(2-(2-ethoxyethyloxy))ethyl phenyl carbonate,1-methyl-1-phenyl(2-methoxy)ethylphenyl carbonate,1-methyl-1-phenyl(2-ethoxy)ethyl phenyl carbonate,1-methyl-1-phenyl(2-propoxy)ethyl phenyl carbonate,1-methyl-1-phenyl(2-butoxy)ethyl phenyl carbonate,1-methyl-1-phenyl(2-isobutyloxy)ethyl phenyl carbonate,1-methyl-1-phenyl(2-benzyloxy)ethyl phenyl carbonate, and1-methyl-1-phenyl(2-(2-ethoxyethyloxy))ethyl phenyl carbonate. Amongthese, one compound, or two or more compounds, selected from(2-ethoxyethyl) methyl carbonate, (2-ethoxyethyl) ethyl carbonate,(2-propoxyethyl) propyl carbonate, (2-butoxyethyl) butyl carbonate,(2-butoxyethyl) ethyl carbonate, (2-ethoxyethyl) propyl carbonate,(2-ethoxyethyl) phenyl carbonate, and (2-ethoxyethyl) p-methylphenylcarbonate are preferable.

Among these, (2-ethoxyethyl) methyl carbonate, (2-ethoxyethyl) ethylcarbonate, and (2-ethoxyethyl) phenyl carbonate are particularlypreferable.

The first internal electron donor compound is particularly preferablyone or more compounds selected from dimethyl diisobutylmalonate, diethyldiisobutylmalonate, dimethyl benzylidenemalonate, and diethylbenzylidenemalonate.

In the first step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the magnesium compound, the tetravalent titanium halidecompound, and one or more first internal electron donor compounds arebrought into contact with each other to effect a reaction, followed bywashing.

In the first step, it is preferable to bring the magnesium compound, thetetravalent titanium halide compound, and the first internal electrondonor compound into contact with each other to effect a reaction in thepresence of an inert organic solvent.

It is preferable to use a compound that is liquid at room temperature(20° C.) and has a boiling point of 50 to 150° C. as the inert organicsolvent. It is more preferable to use an aromatic hydrocarbon compoundor a saturated hydrocarbon compound that is liquid at room temperatureand has a boiling point of 50 to 150° C. as the inert organic solvent.

The inert organic solvent may be one or more compounds selected fromlinear aliphatic hydrocarbon compounds such as hexane, heptane, anddecane, branched aliphatic hydrocarbon compounds such as methylheptane,alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane,and ethylcyclohexane, aromatic hydrocarbon compounds such as toluene,xylene, and ethylbenzene, and the like.

Among these, aromatic hydrocarbon compounds that are liquid at roomtemperature and have a boiling point of 50 to 150° C. are preferablesince the activity of the resulting solid catalyst component and thestereoregularity of the resulting polymer can be improved.

In the first step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the magnesium compound, the tetravalent titanium halidecompound, and the first internal electron donor compound may be broughtinto contact with each other by appropriately mixing the magnesiumcompound, the tetravalent titanium halide compound, and the firstinternal electron donor compound in the presence of the inert organicsolvent.

In the first step, the magnesium compound, the tetravalent titaniumhalide compound, and the first internal electron donor compound arebrought into contact with each other to effect a reaction.

The reaction temperature is preferably 0 to 130° C., more preferably 40to 130° C., still more preferably 30 to 120° C., and yet more preferably80 to 120° C. The reaction time is preferably 1 minute or more, morepreferably 10 minutes or more, still more preferably 30 minutes to 6hours, still more preferably 30 minutes to 5 hours, and yet morepreferably 1 to 4 hours.

In the first step, the components may be subjected to a low-temperatureaging treatment before effecting the reaction.

The low-temperature aging treatment brings the components into contactwith each other (preliminary reaction) at a temperature lower than thereaction temperature. The low-temperature aging temperature ispreferably −20 to 70° C., more preferably −10 to 60° C., and still morepreferably −10 to 30° C. The low-temperature aging time is preferably 1minute to 6 hours, more preferably 5 minutes to 4 hours, and still morepreferably 30 minutes to 3 hours.

When performing the first step that brings the magnesium compound, thetetravalent titanium halide compound, and the first internal electrondonor compound into contact with each other to effect a reaction, thetetravalent titanium halide compound is preferably used in an amount of0.5 to 100 mol, more preferably 1 to 50 mol, and still more preferably 1to 10 mol, based on 1 mol of the magnesium compound.

When performing the first step that brings the magnesium compound, thetetravalent titanium halide compound, and the first internal electrondonor compound into contact with each other to effect a reaction, thefirst internal electron donor compound is preferably used in an amountof 0.01 to 10 mol, more preferably 0.01 to 1 mol, and still morepreferably 0.02 to 0.6 mol, based on 1 mol of the magnesium compound.

When using the inert organic solvent in the first step, the inertorganic solvent is preferably used in an amount of 0.001 to 500 mol,more preferably 0.5 to 100 mol, and still more preferably 1.0 to 20 mol,based on 1 mol of the magnesium compound.

In the first step, it is preferable to bring the components into contactwith each other with stirring in a vessel equipped with a stirrer thatcontains an inert gas atmosphere from which water and the like have beenremoved.

After completion of the reaction, it is preferable to wash the reactionproduct after allowing the reaction mixture to stand, appropriatelyremoving the supernatant liquid to achieve a wet state (slurry state),and optionally drying the reaction mixture by hot-air drying or thelike.

After completion of the reaction, the reaction product is washed afterallowing the reaction mixture to stand, and appropriately removing thesupernatant liquid.

The reaction product is normally washed using a washing agent.

Examples of the washing agent include those mentioned above inconnection with the inert organic solvent that is appropriately used inthe first step. The washing agent is preferably one or more compoundsselected from linear aliphatic hydrocarbon compounds that are liquid atroom temperature and have a boiling point of 50 to 150° C., such ashexane, heptane, and decane, alicyclic hydrocarbon compounds that areliquid at room temperature and have a boiling point of 50 to 150° C.,such as methylcyclohexane and ethylcyclohexane, aromatic hydrocarboncompounds that are liquid at room temperature and have a boiling pointof 50 to 150° C., such as toluene, xylene, ethylbenzene, ando-dichlorobenzene, and the like.

It is possible to easily remove (dissolve) by-products and impuritiesfrom the reaction product by utilizing the washing agent.

In the first step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the reaction product is preferably washed at 0 to 120° C.,more preferably 0 to 110° C., more preferably 30 to 110° C., still morepreferably 50 to 110° C., and yet more preferably 50 to 100° C.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,it is preferable to wash the reaction product by adding the desiredamount of washing agent to the reaction product, stirring the mixture,and removing the liquid phase using a filtration method or a decantationmethod.

When washing the reaction product a plurality of times (two or moretimes) (as described later), the subsequent reaction (i.e., the reactioneffected in the subsequent step) may be effected without removing thewashing agent that was added last to the reaction product.

It is preferable to use the washing agent in the first step in an amountof 1 to 500 mL, more preferably 3 to 200 mL, and still more preferably 5to 100 mL, per gram of the reaction product.

The reaction product may be washed a plurality of times. The reactionproduct is preferably washed 1 to 20 times, more preferably 2 to 15times, and still more preferably 2 to 10 times.

When washing the reaction product a plurality of times, it is preferableto use the washing agent in an amount within the above range each timethe reaction product is washed.

According to the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention, itis possible to remove unreacted raw material components, reactionby-products (e.g., alkoxytitanium halide and titaniumtetrachloride-carboxylic acid complex), and impurities that remain inthe reaction product by washing the reaction product in the first stepafter bringing the components into contact with each other to effect areaction.

In the first step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, a post-treatment may be appropriately performed after washingthe reaction product.

For example, a tetravalent titanium halide compound may be brought intocontact with the reaction product obtained by the reaction, or thereaction product that has been washed, or the reaction product may bewashed after bringing a tetravalent titanium halide compound intocontact with the reaction product. The reaction product may be washedduring the post-treatment in the same manner as described above.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,the reaction product subjected to the post-treatment in the first stepmay be subjected to the second step (described below). Note that it ispreferable to subject the reaction product (that has been washed)directly to the second step without subjecting the reaction product tothe post-treatment.

The product obtained by the first step is normally in the form of asuspension. The product in the form of a suspension may be allowed tostand, and the supernatant liquid may be removed to achieve a wet state(slurry state). The product may optionally be dried by hot-air drying orthe like. The product in the form of a suspension may be subjecteddirectly to the second step. When subjecting the product in the form ofa suspension directly to the second step, the drying treatment can beomitted, and it is unnecessary to add an inert organic solvent in thesecond step.

Second Step

In the second step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, one or more second internal electron donor compounds arebrought into contact with the product obtained by the first step toeffect a reaction.

The second internal electron donor compound used in the second stepincluded in the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention ispreferably one or more compounds selected from organic compounds thatinclude two or more electron donor sites and do not include silicon.Examples of the electron donor site include a hydroxyl group (—OH), acarbonyl group (>C═O), an ether linkage (—OR), an amino group (—NH₂,—NHR, or —NHRR′), a cyano group (—CN), an isocyanate group (—N═C═O), andan amide linkage (—C(═O)NH— or —C(═O)NR—). A carbonyl group (>C═O) maybe those included in an aldehyde group (—(C═O)H), a carboxyl group(—(C═O)OH), a keto group (—(C═O)R), a carbonate group (—O—(C═O)O), anester linkage (—C(C═O)OR), a urethane linkage (—NH—(C═O)O—), and thelike. Among these, esters such as a polycarboxylic acid ester, and ethercompounds such as a diether and an ether carbonate are preferable. Theseinternal electron donor compounds may be used either alone or incombination.

Examples of the polycarboxylic acid ester that may be used in the secondstep include carboxylic acid diesters, and substituted carboxylic aciddiesters in which some of the hydrogen atoms bonded to the carbon atomthat forms the molecular skeleton are substituted with a substituent.

Examples of the carboxylic acid diesters include aromatic dicarboxylicacid diesters such as a phthalic acid diester and an isophthalic aciddiester, aliphatic dicarboxylic acid diesters such as a succinic aciddiester, a maleic acid diester, a malonic acid diester, and a glutaricacid diester, alicyclic dicarboxylic acid diesters such as acycloalkanedicarboxylic acid diester and a cycloalkenedicarboxylic aciddiester, and the like.

Examples of the substituted carboxylic acid diesters includehalogen-substituted carboxylic acid diesters in which a hydrogen atom issubstituted with a halogen atom such as a fluorine atom, a chlorineatom, a bromine atom, or an iodine atom, alkyl-substituted carboxylicacid diesters in which a hydrogen atom is substituted with an alkylgroup having 1 to 8 carbon atoms, alkyl halide-substituted carboxylicacid diesters in which a hydrogen atom is substituted with a halogenatom and an alkyl group having 1 to 8 carbon atoms, and the like.

Specific examples of the substituted carboxylic acid diesters include asubstituted cycloalkanedicarboxylic acid diester in which some of thehydrogen atoms of the cycloalkyl group are substituted with an alkylgroup or the like, a substituted malonic acid diester, analkyl-substituted maleic acid diester, and the like.

Examples of the aromatic dicarboxylic acid diester that may be used asthe second internal electron donor compound include those mentionedabove in connection with the aromatic dicarboxylic acid diesterrepresented by the general formula (V).

Specific examples of the succinic acid diester, the maleic acid diester,the alkyl-substituted maleic acid diester, the malonic acid diester, thesubstituted malonic acid diester, the alkylidenemalonic acid diester,the cycloalkanedicarboxylic acid diester, the substitutedcycloalkanedicarboxylic acid diester (in which some of the hydrogenatoms of the cycloalkyl group are substituted with an alkyl group or thelike), the diether, and the ether carbonate that may be used as thesecond internal electron donor compound include those mentioned above inconnection with the first internal electron donor compound. Note thatthe diether that may be used as the second internal electron donorcompound does not include a silicon atom.

The second internal electron donor compound is particularly preferablyone or more compounds selected from diethyl phthalate, di-n-propylphthalate, di-n-butyl phthalate, diisobutyl phthalate, dimethyldiisobutylmalonate, diethyl diisobutylmalonate, dimethylbenzylidenemalonate, and diethyl benzylidenemalonate.

In the second step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the second internal electron donor compound is brought intocontact with the reaction product obtained by the first step to effect areaction.

In the second step, the second internal electron donor compound maypreferably be brought into contact with the reaction product obtained bythe first step by appropriately mixing the second internal electrondonor compound and the reaction product obtained by the first step inthe presence of an inert organic solvent similar to those mentionedabove in connection with the first step.

In the second step, the components may be brought into contact with eachother under arbitrary conditions. Contact-reaction conditions similar tothose employed in the first step may be used.

When performing the second step that brings the second internal electrondonor compound into contact with the reaction product obtained by thefirst step to effect a reaction, the molar ratio (molar quantity ofsecond internal electron donor compound/molar quantity of magnesiumcompound) of the second internal electron donor compound to themagnesium compound (that is added in the first step) is preferably 0.001to 10, more preferably 0.002 to 1, and still more preferably 0.003 to0.6.

When performing the second step that brings the second internal electrondonor compound into contact with the reaction product obtained by thefirst step to effect a reaction, the molar ratio (molar quantity ofsecond internal electron donor compound/molar quantity of first internalelectron donor compound) of the second internal electron donor compoundto the first internal electron donor compound (that is added in thefirst step) is preferably 0.01 to 0.9, more preferably 0.01 to 0.6, andstill more preferably 0.02 to 0.4.

When the molar ratio (molar quantity of second internal electron donorcompound/molar quantity of first internal electron donor compound) ofthe second internal electron donor compound to the first internalelectron donor compound is within the above range, it is possible toeasily suppress a situation in which a large amount of a complexcompound of the second internal electron donor compound and thetetravalent titanium halide compound is formed, and easily improvepolymerization activity and stereoregularity when polymerizing an olefinusing the resulting solid catalyst component.

When using an inert organic solvent in the second step, the inertorganic solvent is preferably used in an amount of 0.001 to 500 mol,more preferably 0.5 to 100 mol, and still more preferably 1.0 to 20 mol,based on 1 mol of the magnesium compound (that is added in the firststep).

When using an inert organic solvent in the second step, it is possibleto suppress interaction between the third internal electron donorcompound and a tetravalent titanium halide compound, and suppressprecipitation of a complex compound of the third internal electron donorcompound and a tetravalent titanium halide compound in the solidcatalyst component by reducing the amount of tetravalent titanium halidecompound (unreacted tetravalent titanium halide compound) in the inertorganic solvent. Therefore, it is preferable to control theconcentration of a tetravalent titanium halide compound in the inertorganic solvent to 0 to 5 mass %, more preferably 0 to 3 mass %, andstill more preferably 0 to 1 mass %.

Specifically, when implementing the method for producing a solidcatalyst component for olefin polymerization according to one embodimentof the invention, it is desirable to not add a tetravalent titaniumhalide compound in the second step.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,it is preferable to add the necessary amount of the magnesium compoundto the reaction system in the first step, and not add the magnesiumcompound to the reaction system in the second step, taking account ofthe reaction efficiency and the like.

In the second step, it is preferable to bring the components intocontact with each other with stirring in a vessel equipped with astirrer that contains an inert gas atmosphere from which water and thelike have been removed.

After completion of the reaction, it is preferable to wash the reactionproduct after allowing the reaction mixture to stand, appropriatelyremoving the supernatant liquid to achieve a wet state (slurry state),and optionally drying the reaction mixture by hot-air drying or thelike.

It is preferable to wash the resulting reaction product in the secondstep after completion of the reaction.

The reaction product is normally washed using a washing agent. Examplesof the washing agent include those mentioned above in connection withthe first step.

The washing temperature, the washing method, the amount of washingagent, the number of washing operations, and the like employed in thesecond step may be the same as those described above in connection withthe first step.

According to the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention, itis possible to easily remove unreacted raw material components, reactionby-products (e.g., alkoxytitanium halide and titaniumtetrachloride-carboxylic acid complex), and impurities that remain inthe reaction product by washing the reaction product in the second stepafter bringing the components into contact with each other to effect areaction.

In the second step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, a post-treatment may be appropriately performed on thereaction product obtained by the reaction, or the reaction product thathas been washed.

For example, a tetravalent titanium halide compound may be brought intocontact with the reaction product obtained by the reaction, or thereaction product that has been washed, or the reaction product may bewashed after bringing a tetravalent titanium halide compound intocontact with the reaction product. The reaction product may be washedduring the post-treatment in the same manner as described above.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,the reaction product subjected to the post-treatment in the second stepmay be subjected to the third step (described below). Note that it ispreferable to subject the reaction product obtained by the reaction, orthe reaction product that has been washed, directly to the third stepwithout subjecting the reaction product to the post-treatment.

The product obtained by the second step is normally in the form of asuspension. The product in the form of a suspension may be appropriatelyallowed to stand, and the supernatant liquid may be removed to achieve awet state (slurry state). The product may optionally be dried by hot-airdrying or the like. The product in the form of a suspension may besubjected directly to the third step. When subjecting the product in theform of a suspension directly to the third step, the drying treatmentcan be omitted, and it is unnecessary to add an inert organic solvent inthe third step.

Third Step

In the third step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the tetravalent titanium halide compound and one or morethird internal electron donor compounds are brought into contact withthe product obtained by the second step to effect a reaction.

Examples of the tetravalent titanium halide compound used in the thirdstep included in the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the inventioninclude those mentioned above in connection with the tetravalenttitanium halide compound used in the first step.

Examples of the third internal electron donor compound used inconnection with the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the inventioninclude the compounds mentioned above in connection with the secondinternal electron donor compound.

The third internal electron donor compound may be the same as ordifferent from the first internal electron donor compound, and may bethe same as or different from the second internal electron donorcompound.

In the third step included in the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, the tetravalent titanium halide compound and the thirdinternal electron donor compound are brought into contact with thereaction product obtained by the second step to effect a reaction.

In the third step, the tetravalent titanium halide compound and thethird internal electron donor compound may preferably be brought intocontact with the reaction product obtained by the second step byappropriately mixing the tetravalent titanium halide compound, the thirdinternal electron donor compound, and the reaction product obtained bythe second step in the presence of an inert organic solvent similar tothose mentioned above in connection with the first step.

In the third step, the third internal electron donor compound may bebrought into contact with the reaction product obtained by the secondstep under arbitrary conditions. Contact-reaction conditions similar tothose employed in the first step may be used.

When performing the third step that brings the tetravalent titaniumhalide compound and the third internal electron donor compound intocontact with the reaction product obtained by the second step to effecta reaction, the tetravalent titanium halide compound is preferably usedin an amount of 0.1 to 50 mol, more preferably 0.2 to 20 mol, and stillmore preferably 0.3 to 10 mol, based on 1 mol of the magnesium compound(that is added in the first step).

When performing the third step that brings the third internal electrondonor compound into contact with the reaction product obtained by thesecond step to effect a reaction, the molar ratio (molar quantity ofthird internal electron donor compound/molar quantity of magnesiumcompound) of the third internal electron donor compound to the magnesiumcompound (that is added in the first step) is preferably 0.001 to 10,more preferably 0.002 to 1, and still more preferably 0.003 to 0.6.

When performing the third step that brings the tetravalent titaniumhalide compound and the third internal electron donor compound intocontact with the reaction product obtained by the second step to effecta reaction, the molar ratio (molar quantity of third internal electrondonor compound/molar quantity of first internal electron donor compound)of the third internal electron donor compound to the first internalelectron donor compound (that is added in the first step) is preferably0.01 to 0.9, more preferably 0.01 to 0.6, and still more preferably 0.02to 0.4.

When the molar ratio (molar quantity of third internal electron donorcompound/molar quantity of first internal electron donor compound) ofthe third internal electron donor compound to the first internalelectron donor compound is within the above range, it is possible toeasily suppress a situation in which a large amount of a complexcompound of the second internal electron donor compound and thetetravalent titanium halide compound is formed, and easily improvepolymerization activity and stereoregularity when polymerizing an olefinusing the resulting solid catalyst component.

It is preferable that the molar quantity of the third internal electrondonor compound used in the third step be smaller than the molar quantityof the first internal electron donor compound used in the first step,and equal to or smaller than the molar quantity of the second internalelectron donor compound used in the second step (i.e., molar quantity offirst internal electron donor compound>molar quantity of second internalelectron donor compound≧molar quantity of third internal electron donorcompound).

It is preferable that the total molar quantity of the second internalelectron donor compound used in the second step and the third internalelectron donor compound used in the third step be smaller than the molarquantity of the first internal electron donor compound used in the firststep (i.e., molar quantity of first internal electron donorcompound>(molar quantity of second internal electron donorcompound+molar quantity of third internal electron donor compound)).

The molar ratio (total molar quantity of the second internal electrondonor compound used in the second step and the third internal electrondonor compound used in the third step/molar quantity of the firstinternal electron donor compound used in the first step) of the totalmolar quantity of the second internal electron donor compound used inthe second step and the third internal electron donor compound used inthe third step to the molar quantity of the first internal electrondonor compound used in the first step is preferably 0.02 to 0.95, morepreferably 0.02 to 0.9, and still more preferably 0.02 to 0.8.

When the first internal electron donor compound used in the first stepis an aromatic dicarboxylic acid diester, an aliphatic polycarboxylicacid ester, or an alicyclic polycarboxylic acid ester, the secondinternal electron donor compound used in the second step is a carboxylicacid diester, and the third internal electron donor compound used in thethird step is a carboxylic acid diester, the total number of carbonatoms of the ester residue of the first internal electron donorcompound, the total number of carbon atoms of the ester residue of thesecond internal electron donor compound, and the total number of carbonatoms of the ester residue of the third internal electron donor compoundmay be either identical or different.

An internal electron donor compound in which the number of carbon atomsof the ester residue is small normally exhibits high adhesion to acarrier, and allows particles of a solid catalyst component to easilyaggregate. However, a decrease in polymerization activity tends to occurwhen using a solid catalyst component that supports only an internalelectron donor compound in which the number of carbon atoms of the esterresidue is small.

On the other hand, an internal electron donor compound in which thenumber of carbon atoms of the ester residue is large exhibits lowadhesion to a carrier, but improves polymerization activity. Therefore,it is preferable to preferentially incorporate an internal electrondonor compound in which the number of carbon atoms of the ester residueis large and which exhibits low adhesion to a carrier in the solidcatalyst component, and then bring a small amount of an internalelectron donor compound in which the number of carbon atoms of the esterresidue is small and which exhibits high adhesion to a carrier intocontact with the solid catalyst component (optionally by stepwiseaddition) to effect a reaction, since aggregation of the catalystparticles and a decrease in polymerization activity can be suppressed.

When using an inert organic solvent in the third step, the inert organicsolvent is preferably used in an amount of 0.001 to 500 mol, morepreferably 0.5 to 100 mol, and still more preferably 1.0 to 20 mol,based on 1 mol of the magnesium compound (that is added in the firststep).

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,it is preferable to add the necessary amount of the magnesium compoundto the reaction system in the first step, and not add the magnesiumcompound to the reaction system in the third step, taking account of thereaction efficiency and the like.

In the third step, it is preferable to bring the components into contactwith each other with stirring in a vessel equipped with a stirrer thatcontains an inert gas atmosphere from which water and the like have beenremoved.

After completion of the reaction, it is preferable to wash the reactionproduct after allowing the reaction mixture to stand, appropriatelyremoving the supernatant liquid to achieve a wet state (slurry state),and optionally drying the reaction mixture by hot-air drying or thelike.

It is preferable to wash the reaction product in the third step aftercompletion of the reaction.

The reaction product is normally washed using a washing agent. Examplesof the washing agent include those mentioned above in connection withthe first step. The washing temperature, the washing method, the amountof washing agent, the number of washing operations, and the likeemployed in the third step may be the same as those described above inconnection with the first step.

According to the method for producing a solid catalyst component forolefin polymerization according to one embodiment of the invention, itis possible to remove unreacted raw material components, reactionby-products (e.g., alkoxytitanium halide and titaniumtetrachloride-carboxylic acid complex), and impurities that remain inthe reaction product by washing the reaction product in the third stepafter bringing the components into contact with each other to effect areaction.

After completion of the reaction, the suspension obtained by washing maybe appropriately allowed to stand, the supernatant liquid may be removedto achieve a wet state (slurry state), and the reaction mixture mayoptionally be dried by hot-air drying or the like.

The product obtained after washing may be used directly as the solidcatalyst component for olefin polymerization. Alternatively, the productmay be brought into contact with a tetravalent titanium halide compound,washed (post-treatment), and used as the solid catalyst component forolefin polymerization. The product may be washed in the same manner asdescribed above.

The resulting solid catalyst component for olefin polymerization may beformed in the shape of particles using a spray dry method that spraysand dries a solution or a suspension using a sprayer. A spherical solidcatalyst component for olefin polymerization having a sharp particlesize distribution can be easily obtained without using a sphericalmagnesium compound in the first step by forming particles using thespray dry method.

It is preferable to add only small amounts of an aluminum compound and asilicon compound to the reaction system in the second step and the thirdstep, or not add an aluminum compound and a silicon compound to thereaction system in the second step and the third step. In particular, itis preferable to not add an organoaluminum compound such as analkylaluminum and an organosilicon compound such as an alkoxysilane tothe reaction system in the second step and the third step.

If the second step and the third step are performed in the presence ofan organoaluminum compound (e.g., alkylaluminum compound oralkylaluminum halide), a reaction in which the internal electron donorcompound supported on the product is removed easily occurs. If thesecond step and the third step are performed in the presence of asilicon compound (e.g., alkoxysilane), adsorption of the internalelectron donor compound and adsorption of the silicon compound compete,and the desired effects may not be obtained.

The method for producing a solid catalyst component for olefinpolymerization according to one embodiment of the invention maypreferably be implemented as described below.

In the first step, a spherical magnesium compound is suspended in aninert organic solvent to prepare a suspension, and the tetravalenttitanium halide compound is brought into contact with the suspension toeffect a reaction. The first internal electron donor compound is broughtinto contact with the suspension at −20 to 130° C. before or afterbringing the tetravalent titanium halide compound into contact with thesuspension, and the reaction product is washed with an inert organicsolvent to obtain a solid reaction product (α). It is preferable toeffect a low-temperature aging reaction before or after bringing thefirst internal electron donor compound into contact with the suspension.

In the second step, the second internal electron donor compound isbrought into contact with the solid reaction product (α) obtained by thefirst step at 20 to 130° C. (preferably 30 to 120° C., and morepreferably 80 to 110° C.) to effect a reaction, and the reaction productis washed with an inert organic solvent to obtain a solid reactionproduct (β).

In the third step, the tetravalent titanium halide compound and thethird internal electron donor compound are brought into contact with thesolid reaction product (β) obtained by the second step at 20 to 130° C.(preferably 30 to 120° C., and more preferably 80 to 110° C.) in thepresence of an inert organic solvent to effect a reaction to obtain thetarget solid catalyst component for olefin polymerization.

Table 1 shows preferable combinations of the first internal electrondonor compound, the second internal electron donor compound, and thethird internal electron donor compound when implementing the method forproducing a solid catalyst component for olefin polymerization accordingto one embodiment of the invention.

Specifically, (1) a combination of an aromatic dicarboxylic aciddiester, an aromatic dicarboxylic acid diester, and an aromaticdicarboxylic acid diester, (2) a combination of an aromatic dicarboxylicacid diester, an ether carbonate, and an aromatic dicarboxylic aciddiester, (3) a combination of an aromatic dicarboxylic acid diester, analkyl-substituted malonic acid diester, and an alkyl-substituted malonicacid diester, (4) a combination of an alkyl-substituted malonic aciddiester, an alkyl-substituted malonic acid diester, and analkyl-substituted malonic acid diester, (5) a combination of analkyl-substituted malonic acid diester, an alkyl-substituted malonicacid diester, and an ether carbonate, (6) a combination of analkyl-substituted malonic acid diester, an ether carbonate, and analkyl-substituted malonic acid diester, and (7) a combination of analkyl-substituted malonic acid diester, an aromatic carboxylic aciddiester, and aromatic carboxylic acid diester, are preferable as acombination of the first internal electron donor compound, the secondinternal electron donor compound, and the third internal electron donorcompound (see Table 1).

TABLE 1 First internal electron donor Second internal electron Thirdinternal electron donor compound donor compound compound (1) Aromaticdicarboxylic acid Aromatic dicarboxylic acid Aromatic dicarboxylic aciddiester diester diester (2) Aromatic dicarboxylic acid Ether carbonateAromatic dicarboxylic acid diester diester (3) Aromatic dicarboxylicacid Alkyl-substituted malonic Alkyl-substituted malonic diester aciddiester acid diester (4) Alkyl-substituted malonic Alkyl-substitutedmalonic Alkyl-substituted malonic acid diester acid diester acid diester(5) Alkyl-substituted malonic Alkyl-substituted malonic Ether carbonateacid diester acid diester (6) Alkyl-substituted malonic Ether carbonateAlkyl-substituted malonic acid diester acid diester (7)Alkyl-substituted malonic Aromatic dicarboxylic acid Aromaticdicarboxylic acid acid diester diester diester

When any of the above combinations (see (1) to (7)) is used as acombination of the first internal electron donor compound, the secondinternal electron donor compound, and the third internal electron donorcompound when implementing the method for producing a solid catalystcomponent for olefin polymerization according to one embodiment of theinvention, it is possible to easily produce an olefin homopolymer orcopolymer that exhibits a high MFR and excellent stereoregularity.

When implementing the method for producing a solid catalyst componentfor olefin polymerization according to one embodiment of the invention,the contact-reaction operation in the first step may be performed in thepresence of a polysiloxane (i.e., third component).

A polysiloxane is a polymer that includes a siloxane linkage (—Si—O—) inthe main chain, and is also referred to as “silicone oil”. Thepolysiloxane may be a chain-like, partially hydrogenated, cyclic, ormodified polysiloxane that is liquid or viscous at room temperature, andhas a viscosity at 25° C. of 0.02 to 100 cm²/s (2 to 10,000 cSt), andpreferably 0.03 to 5 cm²/s (3 to 500 cSt).

Examples of the chain-like polysiloxane include disiloxanes such ashexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane,hexaphenyldisiloxane, 1,3-divinyltetramethyldisiloxane,1,3-dichlorotetramethyldisiloxane, 1,3-dibromotetramethyldisiloxane,chloromethylpentamethyldisiloxane,1,3-bis(chloromethyl)tetramethyldisiloxane, dimethylpolysiloxane, andmethylphenylpolysiloxane. Examples of the partially hydrogenatedpolysiloxane include methyl hydrogen polysiloxane having a degree ofhydrogenation of 10 to 80%. Examples of the cyclic polysiloxane includehexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, and2,4,6,8-tetramethylcyclotetrasiloxane. Examples of the modifiedpolysiloxane include a higher fatty acid group-substituteddimethylsiloxane, an epoxy group-substituted dimethylsiloxane, and apolyoxyalkylene group-substituted dimethylsiloxane. Among these,decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable,and decamethylcyclopentasiloxane is particularly preferable.

The magnesium atom content in the solid catalyst component for olefinpolymerization obtained by the production method according to oneembodiment of the invention is preferably 10 to 70 mass %, morepreferably 10 to 50 mass %, more preferably 15 to 40 mass %, andparticularly preferably 15 to 25 mass %.

The titanium atom content in the solid catalyst component for olefinpolymerization obtained by the production method according to oneembodiment of the invention is preferably 0.5 to 8.0 mass %, morepreferably 0.5 to 5.0 mass %, and still more preferably 0.5 to 3.0 mass%.

The halogen atom content in the solid catalyst component for olefinpolymerization obtained by the production method according to oneembodiment of the invention is preferably 20 to 88 mass %, morepreferably 30 to 85 mass %, more preferably 40 to 80 mass %, and stillmore preferably 45 to 75 mass %. The content of the first internalelectron donor compound in the solid catalyst component for olefinpolymerization obtained by the production method according to oneembodiment of the invention is preferably 0.1 to 30 mass %, morepreferably 0.3 to 25 mass %, and still more preferably 1.0 to 20 mass %.

The content of the second internal electron donor compound in the solidcatalyst component for olefin polymerization obtained by the productionmethod according to one embodiment of the invention is preferably 0.1 to30 mass %, more preferably 0.3 to 20 mass %, and particularly preferably0.5 to 10 mass %.

The content of the third internal electron donor compound in the solidcatalyst component for olefin polymerization obtained by the productionmethod according to one embodiment of the invention is preferably 0.1 to30 mass %, more preferably 0.3 to 20 mass %, and particularly preferably0.5 to 10 mass %.

The total content of the first internal electron donor compound, thesecond internal electron donor compound, and the third internal electrondonor compound in the solid catalyst component for olefin polymerizationobtained by the production method according to one embodiment of theinvention is preferably 1.5 to 30 mass %, more preferably 3.0 to 25 mass%, and particularly preferably 6.0 to 25 mass %.

The solid catalyst component for olefin polymerization obtained by theproduction method according to one embodiment of the invention exhibitsits performance in a well-balanced manner when the magnesium atomcontent is 15 to 25 mass %, the titanium atom content is 0.5 to 3.0 mass%, the halogen atom content is 45 to 75 mass %, the content of the firstinternal electron donor compound is 2 to 20 mass %, the content of thesecond internal electron donor compound is 0.3 to 10 mass %, the contentof the third internal electron donor compound is 0.3 to 10 mass %, andthe total content of the first internal electron donor compound, thesecond internal electron donor compound, and the third internal electrondonor compound is 6.0 to 25 mass %, for example.

Note that the magnesium atom content in the solid catalyst componentrefers to a value obtained by dissolving the solid catalyst component ina hydrochloric acid solution, and measuring the magnesium atom contentusing an EDTA titration method that utilizes an EDTA solution.

The titanium atom content in the solid catalyst component refers to avalue measured in accordance with the method (oxidation-reductiontitration) specified in JIS M 8311-1997 (“Method for determination oftitanium in titanium ores”).

The halogen atom content in the solid catalyst component refers to avalue obtained by treating the solid catalyst component using a mixtureof sulfuric acid and purified water to obtain an aqueous solution,preparatively isolating a given amount of the aqueous solution, andtitrating halogen atoms with a silver nitrate standard solution (silvernitrate titration method).

The content of the first internal electron donor compound, the contentof the second internal electron donor compound, the content of the thirdinternal electron donor compound, and the total content of the firstinternal electron donor compound, the second internal electron donorcompound, and the third internal electron donor compound in the solidcatalyst component refer to values measured as described later.

The embodiments of the invention thus provide a method that can easilyproduce a novel solid catalyst component for olefin polymerization thatachieves excellent olefin polymerization activity and activity withrespect to hydrogen during polymerization when homopolymerizing orcopolymerizing an olefin, and can produce an olefin polymer thatexhibits a high MFR, high stereoregularity, and excellent rigidity whileachieving high sustainability of polymerization activity.

Olefin Polymerization Catalyst

An olefin polymerization catalyst according to one embodiment of theinvention is described below.

The olefin polymerization catalyst according to one embodiment of theinvention is produced by bringing the solid catalyst component forolefin polymerization obtained by the production method according to oneembodiment of the invention, an organoaluminum compound represented bythe following general formula (I), and an external electron donorcompound into contact with each other.

R¹ _(p)AlQ_(3-p)  (I)

wherein R¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogenatom or a halogen atom, and p is a real number that satisfies 0<p≦3.

The details of the solid catalyst component for olefin polymerizationaccording to one embodiment of the invention have been described above.

R¹ in the organoaluminum compound represented by the general formula (I)is an alkyl group having 1 to 6 carbon atoms. Specific examples of thealkyl group having 1 to 6 carbon atoms represented by R¹ include amethyl group, an ethyl group, a n-propyl group, an isopropyl group, an-butyl group, an isobutyl group, and the like.

Q in the organoaluminum compound represented by the general formula (I)is a hydrogen atom or a halogen atom. Specific examples of the halogenatom represented by Q include a fluorine atom, a chlorine atom, abromine atom, and an iodine atom.

Specific examples of the organoaluminum compound represented by thegeneral formula (I) include one or more compounds selected fromtriethylaluminum, diethylaluminum chloride, triisobutylaluminum,diethylaluminum bromide, and diethylaluminum hydride. Among these,triethylaluminum and triisobutylaluminum are preferable.

Examples of the external electron donor compound used to produce theolefin polymerization catalyst according to one embodiment of theinvention include organic compounds that include an oxygen atom or anitrogen atom. Examples of the organic compounds that include an oxygenatom or a nitrogen atom include alcohols, phenols, ethers, esters,ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates,and organosilicon compounds. The external electron donor compound may bean organosilicon compound that includes a Si—O—C linkage, an aminosilanecompound that includes a Si—N—C linkage, or the like.

Among these, esters such as ethyl benzoate, ethyl p-methoxybenzoate,ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methylanisate, and ethyl anisate, 1,3-diethers, organosilicon compounds thatinclude an Si—O—C linkage, and aminosilane compounds that include anSi—N—C linkage are preferable, and organosilicon compounds that includean Si—O—C linkage, and aminosilane compounds that include an Si—N—Clinkage are particularly preferable.

Examples of the organosilicon compound that includes an Si—O—C linkageand may be used as the external electron donor compound include anorganosilicon compound represented by the following general formula(II).

R²Si(OR³)_(4-q)  (II)

wherein R² is an alkyl group having 1 to 12 carbon atoms, a cycloalkylgroup having 3 to 12 carbon atoms, a phenyl group, a vinyl group, anallyl group, or an aralkyl group, provided that a plurality of R² areeither identical or different when a plurality of R² are present, R³ isan alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, or anaralkyl group, provided that a plurality of R³ are either identical ordifferent when a plurality of R³ are present, and q is an integer from 0to 3.

Examples of the aminosilane compound that includes an Si—N—C linkage andmay be used as the external electron donor compound include anorganosilicon compound represented by the following general formula(III).

(R⁴R⁵N)_(s)SiR⁶ _(4-s)  (III)

wherein R⁴ and R⁵ are a hydrogen atom, a linear alkyl group having 1 to20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, avinyl group, an allyl group, an aralkyl group, a cycloalkyl group having3 to 20 carbon atoms, or an aryl group, provided that R⁴ and R⁵ areeither identical or different, and optionally bond to each other to forma ring, R⁶ is a linear alkyl group having 1 to 20 carbon atoms, abranched alkyl group having 3 to 20 carbon atoms, a vinyl group, anallyl group, an aralkyl group, a linear or branched alkoxy group having1 to 20 carbon atoms, a vinyloxy group, an allyloxy group, a cycloalkylgroup having 3 to 20 carbon atoms, an aryl group, or an aryloxy group,provided that a plurality of R⁶ are either identical or different when aplurality of R⁶ are present, and s is an integer from 1 to 3.

Examples of the organosilicon compound represented by the generalformula (II) or (III) include phenylalkoxysilanes, alkylalkoxysilanes,phenylalkylalkoxysilanes, cycloalkylalkoxysilanes,alkyl(cycloalkyl)alkoxysilanes, (alkylamino)alkoxysilanes,alkyl(alkylamino)alkoxysilanes, cycloalkyl(alkylamino)alkoxysilanes,tetraalkoxysilanes, tetrakis(alkylamino)silanes,alkyltris(alkylamino)silanes, dialkylbis(alkylamino)silanes,trialkyl(alkylamino)silanes, and the like. Specific examples of theorganosilicon compound represented by the general formula (II) or (III)include n-propyltriethoxysilane, cyclopentyltriethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane, t-butyltrimethoxysilane,diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane,diisopentyldimethoxysilane, bis(2-ethylhexyl)dimethoxysilane,t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane,dicyclopentyldimethoxysilane, dicyclohexyldimetoxysilane,cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane,tetraethoxysilane, tetrabutoxysilane, bis(ethylamino)methylethylsilane,bis(ethylamino)-t-butylmethylsilane, bis(ethylamino)dicyclohexylsilane,dicyclopentylbis(ethylamino)silane,bis(methylamino)(methylcyclopentylamino)methylsilane,diethylaminotriethoxysilane, bis(cyclohexylamino)dimethoxysilane,bis(perhydroisoquinolino)dimethoxysilane,bis(perhydroquinolino)dimethoxysilane,ethyl(isoquinolino)dimethoxysilane, and the like. For example, one ormore compounds selected from n-propyltriethoxysilane,phenyltrimethoxysilane, t-butylmethyldimethoxysilane,t-butylethyldimethoxysilane, diisopropyldimethoxysilane,isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane,diphenyldimethoxysilane, dicyclopentyldimethoxysilane,cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane,t-butylmethylbis(ethylamino)silane, bis(ethylamino)dicyclohexylsilane,dicyclopentylbis(ethylamino)silane,bis(perhydroisoquinolino)dimethoxysilane, diethylaminotriethoxysilane,and the like may be used.

The solid catalyst component for olefin polymerization obtained by theproduction method according to one embodiment of the invention, theorganoaluminum compound, and the external electron donor compound may beused to produce the olefin polymerization catalyst according to oneembodiment of the invention in an arbitrary ratio as long as theadvantageous effects of the invention can be achieved. Theorganoaluminum compound is preferably used in an amount of 1 to 2000mol, and more preferably 50 to 1000 mol, per mol of the titanium atomsincluded in the solid catalyst component for olefin polymerizationobtained by the production method according to one embodiment of theinvention. The external electron donor compound is preferably used in anamount of 0.002 to 10 mol, more preferably 0.01 to 2 mol, and still morepreferably 0.01 to 0.5 mol, per mol of the organoaluminum compound.

The olefin polymerization catalyst according to one embodiment of theinvention may be produced by bringing (a) the solid catalyst componentfor olefin polymerization obtained by the production method according toone embodiment of the invention, (β) the organoaluminum compound, and(γ) the external electron donor compound into contact with each otherusing a known method.

The components may be brought into contact with each other in anarbitrary order. For example, the components may be brought into contactwith each other in any of the orders shown below.

(i) Solid catalyst component (α)→external electron donor compound(γ)→organoaluminum compound (β)(ii) Organoaluminum compound (β)→external electron donor compound(γ)→solid catalyst component (α)(iii) External electron donor compound (γ)→solid catalyst component(α)→organoaluminum compound (β)(iv) External electron donor compound (γ)→organoaluminum compound(β)→solid catalyst component (α)

It is preferable to bring the components into contact with each otheraccording to the contact order example (ii).

Note that the symbol “→” in the contact order examples (i) to (iv)indicates the contact order. For example, “solid catalyst component(α)→organoaluminum compound (β)→external electron donor compound (γ)”means that the organoaluminum compound (β) is brought into contact with(added to) the solid catalyst component (α), and the external electrondonor (γ) is brought into contact with the mixture.

The olefin polymerization catalyst according to one embodiment of theinvention may be produced by bringing the solid catalyst component forolefin polymerization obtained by the production method according to oneembodiment of the invention, the organoaluminum compound, and theexternal electron donor compound into contact with each other in theabsence of an olefin, or may be produced by bringing the solid catalystcomponent for olefin polymerization obtained by the production methodaccording to one embodiment of the invention, the organoaluminumcompound, and the external electron donor compound into contact witheach other in the presence of an olefin (i.e., in the polymerizationsystem).

The embodiments of the invention thus provide a novel olefinpolymerization catalyst that achieves excellent olefin polymerizationactivity and activity with respect to hydrogen during polymerizationwhen homopolymerizing or copolymerizing an olefin, and can produce anolefin polymer that exhibits a high MFR, high stereoregularity, andexcellent rigidity while achieving high sustainability of polymerizationactivity.

A method for producing an olefin polymer according to one embodiment ofthe invention is described below.

The method for producing an olefin polymer according to one embodimentof the invention includes polymerizing an olefin in the presence of theolefin polymerization catalyst according to one embodiment of theinvention.

The olefin that is polymerized using the method for producing an olefinpolymer according to one embodiment of the invention may be one or moreolefins selected from ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, vinylcyclohexane, and the like. Among these,ethylene, propylene, and 1-butene are preferable, and propylene is morepreferable.

Propylene may be copolymerized with another olefin. It is preferable tosubject propylene and another α-olefin to block copolymerization. Ablock copolymer obtained by block copolymerization is a polymer thatincludes two or more segments in which the monomer composition changessequentially. A block copolymer obtained by block copolymerization has astructure in which two or more polymer chains (segments) that differ inpolymer primary structure (e.g., type of monomer, type of comonomer,comonomer composition, comonomer content, comonomer arrangement, andstereoregularity) are linked within one molecular chain.

The olefin that is copolymerized with propylene is preferably anα-olefin having 2 to 20 carbon atoms (excluding propylene having 3carbon atoms). Specific examples of the olefin include ethylene,1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like.These olefins may be used either alone or in combination. In particular,ethylene and 1-butene are preferably used.

The olefin may be polymerized using the method for producing an olefinpolymer according to one embodiment of the invention in the presence orabsence of an organic solvent.

The olefin may be polymerized in a gaseous state or a liquid state.

The olefin is polymerized in a reactor (e.g., autoclave) in the presenceof the olefin polymerization catalyst according to one embodiment of theinvention with heating and pressurizing, for example.

When implementing the method for producing an olefin polymer accordingto one embodiment of the invention, the polymerization temperature isnormally 200° C. or less, preferably 100° C. or less. The polymerizationtemperature is preferably 60 to 100° C., and more preferably 70 to 90°C., from the viewpoint of improving activity and stereoregularity. Whenimplementing the method for producing an olefin polymer according to oneembodiment of the invention, the polymerization pressure is preferably10 MPa or less, and more preferably 5 MPa or less.

A continuous polymerization method or a batch polymerization method maybe used. The olefin may be polymerized in a single step, or may bepolymerized in two or more steps.

When implementing the method for producing an olefin polymer accordingto one embodiment of the invention, block copolymerization of propyleneand another olefin may normally be effected by polymerizing propylene,or copolymerizing propylene and a small amount of α-olefin (e.g.,ethylene) in the first step, and copolymerizing propylene and anα-olefin (e.g., ethylene) in the second step in the presence of theolefin polymerization catalyst according to one embodiment of theinvention. Note that the first-step polymerization reaction may berepeatedly effected a plurality of times, and the second-steppolymerization reaction may be repeatedly effected a plurality of times(i.e., multistep reaction).

More specifically, block copolymerization of propylene and anotherolefin may be effected by effecting first-step polymerization whileadjusting the polymerization temperature and the polymerization time sothat the resulting polypropylene part accounts for 20 to 90 wt % of thefinal copolymer, introducing propylene and ethylene or another α-olefinin the second step, and polymerizing the components so that the rubberpart (e.g., ethylene-propylene rubber (EPR)) accounts for 10 to 80 wt %of the final copolymer.

The polymerization temperature in the first step and the second step ispreferably 200° C. or less, and more preferably 100° C. or less. Thepolymerization pressure in the first step and the second step ispreferably 10 MPa or less, and more preferably 5 MPa or less.

The copolymerization reaction may be effected using a continuouspolymerization method or a batch polymerization method. Thepolymerization reaction may be effected in one step, or may be effectedin two or more steps.

The polymerization time (i.e., the residence time in the reactor) ineach polymerization step, or the polymerization time when using acontinuous polymerization method, is preferably 1 minute to 5 hours.

Examples of the polymerization method include a slurry polymerizationmethod that utilizes an inert hydrocarbon solvent such as cyclohexane orheptane, a bulk polymerization method that utilizes a solvent such asliquefied propylene, and a gas-phase polymerization method in which asolvent is not substantially used. Among these, a bulk polymerizationmethod and a gas-phase polymerization method are preferable. It ispreferable to use a gas-phase polymerization method in the second stepin order to suppress elution from the polypropylene (PP) particlesincluded in EPR.

When implementing the method for producing an olefin polymer accordingto one embodiment of the invention, preliminary polymerization may beeffected by bringing part or all of the components of the olefinpolymerization catalyst according to one embodiment of the inventioninto contact with the olefin before polymerizing the olefin (hereinaftermay be appropriately referred to as “main polymerization”).

The components of the olefin polymerization catalyst according to oneembodiment of the invention may be brought into contact with the olefinin an arbitrary order when effecting the preliminary polymerization. Itis preferable to add the organoaluminum compound to a preliminarypolymerization system that contains an inert gas atmosphere or an olefingas atmosphere, add the solid catalyst component for olefinpolymerization according to one embodiment of the invention to thepreliminary polymerization system, and bring one or more olefins (e.g.,propylene) into contact with the mixture. It is also preferable to addthe organoaluminum compound to a preliminary polymerization system thatcontains an inert gas atmosphere or an olefin gas atmosphere, add theexternal electron donor compound to the preliminary polymerizationsystem, add the solid catalyst component for olefin polymerizationaccording to one embodiment of the invention to the preliminarypolymerization system, and bring one or more olefins (e.g., propylene)into contact with the mixture.

The olefin subjected to the main polymerization, or a monomer such asstyrene may be used for the preliminary polymerization. The preliminarypolymerization conditions may be the same as the above polymerizationconditions.

It is possible to improve the catalytic activity, and easily improve thestereoregularity, the particle properties, and the like of the resultingpolymer by effecting the preliminary polymerization.

The embodiments of the invention thus provide a novel method that canproduce an olefin polymer that exhibits a high MFR, highstereoregularity, and excellent rigidity while achieving highsustainability of polymerization activity.

The invention is further described below by way of examples. Note thatthe following examples are for illustration purposes only, and theinvention is not limited to the following examples.

In the examples and comparative examples, the sphericity of thedialkoxymagnesium particles, and the content of magnesium atoms,titanium atoms, halogen atoms, and the internal electron donor compoundin the solid catalyst component were measured as described below.

Sphericity of Dialkoxymagnesium Particles

The sphericity of the dialkoxymagnesium particles was determined byphotographing the dialkoxymagnesium particles using a scanning electronmicroscope (“JSM-7500F” manufactured by JEOL Ltd.) at a magnification atwhich 500 to 1000 dialkoxymagnesium particles were displayed on ascreen, randomly sampling 500 or more dialkoxymagnesium particles fromthe photographed dialkoxymagnesium particles, determining the area S andthe circumferential length L of each dialkoxymagnesium particle usingimage analysis software (“MacView Ver. 4.0” manufactured by MOUNTECHCo., Ltd.), calculating the sphericity of each dialkoxymagnesiumparticle using the following expression, and calculating the arithmeticmean value.

Sphericity of each dialkoxymagnesium particle=4π×S÷L ²

Content of Magnesium Atoms in Solid Catalyst Component

The solid catalyst component from which the solvent component had beencompletely removed by heating (drying) under reduced pressure wasweighed, and dissolved in a hydrochloric acid solution. After theaddition of methyl orange (indicator) and a saturated ammonium chloridesolution, the mixture was neutralized with aqueous ammonia, heated,cooled, and filtered to remove a precipitate (titanium hydroxide). Agiven amount of the filtrate was isolated preparatively, and heated.After the addition of a buffer and an EBT mixed indicator, magnesiumatoms were titrated using an EDTA solution to determine the content ofmagnesium atoms in the solid catalyst component (EDTA titration method).

Content of Titanium Atoms in Solid Catalyst Component

The content of titanium atoms in the solid catalyst component wasdetermined in accordance with the method (oxidation-reduction titration)specified in JIS M 8311-1997 (“Method for determination of titanium intitanium ores”).

Content of Halogen Atoms in Solid Catalyst Component

The solid catalyst component from which the solvent component had beencompletely removed by heating (drying) under reduced pressure wasweighed, and treated with a mixture of sulfuric acid and purified waterto obtain an aqueous solution. A given amount of the aqueous solutionwas isolated preparatively, and halogen atoms were titrated with asilver nitrate standard solution using an automatic titration device(“COM-1500” manufactured by Hiranuma Sangyo Co., Ltd.) to determine thecontent of halogen atoms in the solid catalyst component (silver nitratetitration method).

Content of Internal Electron Donor Compound in Solid Catalyst Component

The content of the internal electron donor compound (first internalelectron donor compound, second internal electron donor compound, andthird internal electron donor compound) in the solid catalyst componentwas determined using a gas chromatograph (“GC-14B” manufactured byShimadzu Corporation) under the following conditions. The number ofmoles of each component (each internal electron donor compound) wascalculated from the gas chromatography measurement results using acalibration curve that was drawn in advance using the measurementresults at a known concentration.

Measurement Conditions

Column: packed column (2.6 (diameter)×2.1 m, Silicone SE-30 10%,Chromosorb WAW DMCS 80/100, manufactured by GL Sciences Ltd.)Detector: flame ionization detector (FID)Carrier gas: helium, flow rate: 40 ml/minMeasurement temperature: vaporization chamber: 280° C., column: 225° C.,detector: 280° C., or vaporization chamber: 265° C., column: 180° C.,detector: 265° C.

Example 1 Production of Solid Catalyst Component (1) First Step

A 500 ml round bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565mmol) of toluene to prepare a solution.

A suspension prepared using 20 g (175 mmol) of sphericaldiethoxymagnesium (sphericity (l/w): 1.10), 80 ml (753 mmol) of toluene,and 1.8 ml (7.8 mmol) of di-n-propyl phthalate was added to thesolution. The mixture was stirred at −5° C. for 1 hour, and heated to110° C. 5.4 ml (23.4 mmol) of di-n-propyl phthalate was added stepwiseto the mixture while heating the mixture. After reacting the mixture at110° C. for 2 hours with stirring, the resulting reaction mixture wasallowed to stand, and the supernatant liquid was removed to obtain areaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product. After the addition of 170 ml (1600 mmol)of toluene and 30 ml (273 mmol) of titanium tetrachloride, the mixturewas heated to 110° C., and reacted for 2 hours with stirring. Theresulting reaction mixture was allowed to stand, and the supernatantliquid was removed to obtain a reaction product slurry including a solidcomponent (I).

(2) Second Step

Toluene was added to the reaction product slurry including the solidcomponent (I) to adjust the concentration of titanium tetrachloride inthe reaction mixture to 0.2 mass %, and the mixture was heated whileadding 0.4 ml (2.5 mmol) of 2-ethoxyethyl ethyl carbonate. The mixturewas reacted at 100° C. for 1 hour with stirring. The resulting reactionmixture was allowed to stand, and the supernatant liquid was removed toobtain a reaction product slurry including a solid component (II).

(3) Third Step

170 ml (1600 mmol) of toluene and 30 ml (273 mmol) of titaniumtetrachloride were added to the reaction product slurry including thesolid component (II). The mixture was heated to 110° C., and reacted for1 hour with stirring. After completion of the reaction, the supernatantliquid (toluene) was removed. After the addition of 180 ml of tolueneand 20 ml (182 mmol) of titanium tetrachloride, the mixture was heated.After the addition of 0.4 ml (2.5 mmol) of 2-ethoxyethyl ethylcarbonate, the mixture was reacted at 110° C. for 2 hours with stirring.The resulting reaction mixture was allowed to stand, and the supernatantliquid was removed to obtain a reaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated twice. Afterthe addition of 150 ml of n-heptane (60° C.) to the resulting reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated five timesto wash the reaction product to obtain about 20 g of a solid catalystcomponent (A1) for olefin polymerization.

The solid catalyst component (A1) had a magnesium atom content of 20.3mass %, a titanium atom content of 1.3 mass %, a halogen atom content of61.2 mass %, a total internal electron donor compound content of 15.8mass %, and a 2-ethoxyethyl ethyl carbonate content of 1.9 mass %.

Preparation of Propylene Polymerization Catalyst and Polymerization ofPropylene

An autoclave (internal volume: 2.0 l) equipped with a stirrer in whichthe internal atmosphere had been completely replaced by nitrogen gas,was charged with 1.32 mmol of triethylaluminum, 0.13 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and the solid catalystcomponent (A1) (0.0013 mmol on a titanium atom basis) to prepare anolefin polymerization catalyst.

The autoclave was charged with 9.0 l of hydrogen gas and 1.4 l ofliquefied propylene. The liquefied propylene was subjected topreliminary polymerization at 20° C. for 5 minutes under a pressure of1.1 MPa, heated, and polymerized at 70° C. for 1 hour under a pressureof 3.5 MPa to obtain a propylene polymer (polypropylene).

The propylene polymerization activity per gram of the solid catalystcomponent, the melt flow rate (MFR) of the polymer, the p-xylene-solublecontent (XS) in the polymer, and the isotactic pentad fraction(NMR-mmmm) of the polymer were measured as described below. The resultsare shown in Table 2.

Propylene Polymerization Activity

The propylene polymerization activity per gram of the solid catalystcomponent was calculated using the following expression.

Propylene polymerization activity (kg-pp/g-catalyst)=mass (kg) ofpolypropylene/mass (g) of solid catalyst component included in olefinpolymerization catalyst

Melt Flow Rate (MFR) of Polymer

The melt flow rate (MFR) (melt flow index) (g/10 min) of the polymer wasmeasured in accordance with ASTM D1238 (JIS K 7210).

Xylene-Soluble Content (XS) in Polymer

A flask equipped with a stirrer was charged with 4.0 g of the polymer(polypropylene) and 200 ml of p-xylene. The external temperature wasincreased to be equal to or higher than the boiling point (about 150°C.) of xylene, and the polymer was dissolved over 2 hours whilemaintaining p-xylene contained in the flask at a temperature (137 to138° C.) under the condition of boiling point. The solution was cooledto 23° C. over 1 hour, and an insoluble component and a solublecomponent were separated by filtration. A solution of the solublecomponent was collected, and p-xylene was evaporated by heating (drying)under reduced pressure. The weight of the residue was calculated, andthe relative ratio (mass %) with respect to the polymer (propylene) wascalculated to determine the xylene-soluble content (XS).

Isotactic Pentad Fraction (NMR-mmmm) of Polymer

The term “isotactic pentad fraction (NMR-mmmm)” refers to the fraction(%) of a propylene monomer unit situated at the center of an isotacticchain (i.e., a chain in which five propylene monomer units aresequentially meso-linked) of a pentad unit in a polypropylene molecularchain that is measured by the method described in A. Zambelli et al.,Macromolecules, 6, 925 (1973). The isotactic pentad fraction (NMR-mmmm)is calculated using ¹³C-NMR. The area fraction of the mmmm peak withrespect to the total absorption peaks in the methyl-carbon region of the¹³C-NMR spectrum was calculated, and taken as the isotactic pentadfraction.

The isotactic pentad fraction (NMR-mmmm) of the polymer was determinedby performing ¹³C-NMR measurement using an NMR device (“JNM-ECA400”manufactured by JEOL Ltd.) under the following conditions.

¹³C-NMR Measurement Conditions

Measurement mode: proton decoupling methodPulse width: 7.25 μsecPulse repetition time: 7.4 secIntegration count: 10,000Solvent: tetrachloroethane-d2Sample concentration: 200 mg/3.0 ml

Flexural Modulus (FM)

The polymer was injection-molded to prepare a property measurementspecimen. The specimen was conditioned in a temperature-controlled roommaintained at 23° C. for 144 hours or more, and in accordance with JIS K7171, the flexural modulus (FM) (MPa) was measured using the specimenprovided that a liquid/powder exudate was not observed on the surfacethereof.

Preparation of Copolymerization Catalyst and Ethylene-Propylene BlockCopolymerization

A copolymerization catalyst was prepared as described below using thesolid catalyst component (A1), and a copolymer was produced by multisteppolymerization as described below. The ethylene-propylene blockcopolymerization activity (ICP (impact copolymer) polymerizationactivity) during copolymerization was measured as described below toevaluate the sustainability of polymerization activity, and the blockratio, the flexural modulus (FM), and the Izod impact strength of theresulting ethylene-propylene block copolymer were measured.

An autoclave (internal volume: 2.0 l) equipped with a stirrer in whichthe internal atmosphere had been completely replaced by nitrogen gas,was charged with 2.4 mmol of triethylaluminum, 0.24 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and the solid catalystcomponent (A1) (0.003 mmol on a titanium atom basis) to prepare anethylene-propylene copolymerization catalyst (B1).

The autoclave containing the ethylene-propylene copolymerizationcatalyst (B1) was charged with liquefied propylene (15 mol) and hydrogengas (partial pressure: 0.20 MPa). The liquefied propylene was subjectedto preliminary polymerization at 20° C. for 5 minutes, and subjected tofirst-step propylene polymerization (homopolymerization) at 70° C. for75 minutes. The pressure inside the autoclave was then returned tonormal pressure. After replacing the internal atmosphere of theautoclave by nitrogen, the autoclave was weighed. After feedingethylene, propylene, and hydrogen to the autoclave in a molar ratio of1.0/1.0/0.043, the mixture was heated to 70° C., and reacted at 70° C.for 1 hour under a pressure of 1.2 MPa while feeding ethylene,propylene, and hydrogen in a ratio of 2/2/0.086 (1/min) to obtain anethylene-propylene copolymer.

The ethylene-propylene copolymerization activity (kg-ICP/(g-cat·hr)) wasmeasured as described below, the flexural modulus (FM) of theethylene-propylene copolymer was measured as described above, and theblock ratio (mass %), and the Izod impact strength of theethylene-propylene copolymer were measured as described below. Theresults are shown in Table 3.

Ethylene-Propylene Block Copolymerization Activity (ICP Activity)(Kg-ICP/(g-cat·hr))

The ethylene-propylene block copolymerization activity (ICP activity)when producing the ethylene-propylene block copolymer was calculatedusing the following expression.

Ethylene-propylene block copolymerization activity(kg-ICP/(g-cat·hr))=((I(kg)−G (kg))/mass (g) of solid catalyst componentincluded in olefin polymerization catalyst)/1.0 (hr)

Note that I is the mass (kg) of the autoclave after completion ofcopolymerization, and G is the mass (kg) of the autoclave afterunreacted monomers had been removed after completion of homo-PPpolymerization.

Block Ratio (Mass %)

The block ratio of the copolymer was calculated using the followingexpression.

Block ratio(mass %)={(I(kg)−G(kg))/(I(kg)−F(kg))}×100

Note that I is the mass (kg) of the autoclave after completion ofcopolymerization, G is the mass (kg) of the autoclave after unreactedmonomers had been removed after completion of homo-PP polymerization,and F is the mass (kg) of the autoclave.

Izod Impact Strength

0.10 wt % of IRGANOX 1010 (manufactured by BASF), 0.10 wt % of IRGAFOS168 (manufactured by BASF), and 0.08 wt % of calcium stearate were addedto the ethylene-propylene copolymer, and the mixture was kneaded andgranulated using a single-screw extruder to obtain pellets of theethylene-propylene copolymer.

The pellets of the ethylene-propylene copolymer were introduced into aninjection molding machine (mold temperature: 60° C., cylindertemperature: 230° C.), and injection-molded to prepare a propertymeasurement specimen.

The specimen was conditioned in a temperature-controlled room maintainedat 23° C. for 144 hours or more, and the Izod impact strength (23° C.and −30° C.) of the specimen was measured in accordance with JIS K 7110(“Method of Izod impact test for rigid plastics”) using an Izod tester(“Model A-121804405” manufactured by Toyo Seiki Seisaku-Sho, Ltd.).

Shape of specimen: ISO 180/4A, thickness: 3.2 mm, width: 12.7 mm,length: 63.5 mm Shape of notch: type-A notch (radius: 0.25 mm) formedusing a die provided with a notch

Temperature: 23° C. and −30° C.

Impact speed: 3.5 m/sNominal pendulum energy: 5.5 J (23° C.) and 2.75 J (−30° C.)

Example 2

About 20 g of a solid catalyst component (A2) for olefin polymerizationwas produced in the same manner as in Example 1, except that 0.5 ml (2.2mmol) of di-n-propyl phthalate was used in the third step instead of 0.4ml (2.5 mmol) of 2-ethoxyethyl ethyl carbonate.

The solid catalyst component (A2) had a magnesium atom content of 20.3mass %, a titanium atom content of 1.6 mass %, a halogen atom content of60.5 mass %, a total internal electron donor compound content of 16.1mass %, and a 2-ethoxyethyl ethyl carbonate content of 1.1 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example1, except that the solid catalyst component (A2) was used instead of thesolid catalyst component (A1), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 1. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 2 and 3.

Example 3

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example2 using the solid catalyst component (A2) obtained in Example 2, exceptthat 0.13 mmol or 0.24 mmol of dicyclopentylbis(ethylamino)silane(DCPEAS) was used instead of 0.13 mmol or 0.24 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 2. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 2 and 3.

Example 4

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example2 using the solid catalyst component (A2) obtained in Example 2, exceptthat 0.13 mmol or 0.24 mmol of diethylaminotriethoxysilane (DEATES) wasused instead of 0.13 mmol or 0.24 mmol ofcyclohexylmethyldimethoxysilane (CMDMS), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 2. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 2 and 3.

Example 5

About 20 g of a solid catalyst component (A3) for olefin polymerizationwas produced in the same manner as in Example 2, except that the amountof 2-ethoxyethyl ethyl carbonate added in the second step was changedfrom 0.4 ml (2.5 mmol) to 0.6 ml (3.7 mmol), and the amount ofdi-n-propyl phthalate added in the third step was changed from 0.5 ml(2.2 mmol) to 0.6 ml (2.6 mmol).

The solid catalyst component (A3) had a magnesium atom content of 19.9mass %, a titanium atom content of 1.3 mass %, a halogen atom content of61.3 mass %, a total internal electron donor compound content of 15.7mass %, and a 2-ethoxyethyl ethyl carbonate content of 2.0 mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 1, except that the solidcatalyst component (A3) was used instead of the solid catalyst component(A1), and the propylene polymerization activity and the resultingpolymer were evaluated. The results are shown in Table 2.

Example 6

A solid catalyst component (A4) was produced in the same manner as inExample 2, except that 3,3-bis(methoxymethyl)-2,6-dimethylheptane(equimolar amount) was used in the second step instead of 0.4 ml (2.5mmol) of 2-ethoxyethyl ethyl carbonate.

The solid catalyst component (A4) had a magnesium atom content of 20.4mass %, a titanium atom content of 1.3 mass %, a halogen atom content of60.8 mass %, a total internal electron donor compound content of 14.6mass %, and a 3,3-bis(methoxymethyl)-2,6-dimethylheptane content of 1.8mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 1, except that the solidcatalyst component (A4) was used instead of the solid catalyst component(A1), and the propylene polymerization activity and the resultingpolymer were evaluated. The results are shown in Table 2.

Example 7

A solid catalyst component (A5) was produced in the same manner as inExample 6, except that 3,3-bis(methoxymethyl)-2,6-dimethylheptane(equimolar amount) was used in the third step instead of 0.5 ml (2.2mmol) of di-n-propyl phthalate. The solid catalyst component (A5) had amagnesium atom content of 20.2 mass %, a titanium atom content of 1.2mass %, a halogen atom content of 61.6 mass %, a total internal electrondonor compound content of 15.3 mass %, and a3,3-bis(methoxymethyl)-2,6-dimethylheptane content of 3.7 mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 1, except that the solidcatalyst component (A5) was used instead of the solid catalyst component(A1), and the propylene polymerization activity and the resultingpolymer were evaluated. The results are shown in Table 2.

Example 8 Production of Solid Catalyst Component (1) First Step

A 500 ml round-bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 120 ml (819 mmol) of n-heptane. After the addition of 15 g(158 mmol) of anhydrous magnesium chloride and 106 ml (274 mmol) oftetrabutoxytitanium, the mixture was reacted at 90° C. for 1.5 hours toobtain a homogenous solution. After cooling the solution to 40° C., 24ml (88 mmol) of methyl hydrogen polysiloxane (20 cSt) was added to thesolution while maintaining the temperature of the solution at 40° C.,and a precipitation reaction was effected for 5 hours. The resultingreaction mixture was allowed to stand, the supernatant liquid wasremoved to obtain a reaction product slurry, and the reaction productwas sufficiently washed with n-heptane.

A 500 ml round-bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 40 g of the reaction product, and n-heptane was added tothe flask so that the concentration of the reaction product was 200mg/ml. After the addition of 12 ml (105 mmol) of SiCl₄, the mixture wasreacted at 90° C. for 3 hours. The resulting reaction mixture wasallowed to stand, the supernatant liquid was removed to obtain areaction product slurry, and the reaction product was sufficientlywashed with n-heptane.

After the addition of n-heptane so that the concentration of thereaction product was 100 mg/ml, 20 ml (182 mmol) of TiCl₄ was added tothe mixture. After the addition of 7.2 ml (27.1 mmol) of dibutylphthalate, the mixture was reacted at 95° C. for 3 hours. The resultingreaction mixture was allowed to stand, and the supernatant liquid wasremoved to obtain a reaction product slurry.

After the addition of 120 ml of n-heptane to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated seven timesto wash the reaction product to obtain a reaction product slurryincluding a solid component (I).

(2) Second Step

100 ml (695 mmol) of n-heptane was added to the reaction product slurryincluding the solid component (I). After the addition of 0.6 ml (3.8mmol) of 2-ethoxyethyl ethyl carbonate, the mixture was reacted at 95°C. for 3 hours. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurryincluding a solid component (II).

(3) Third Step

187 ml (1760 mmol) of toluene and 20 ml (182 mmol) of titaniumtetrachloride were added to the reaction product slurry including thesolid component (II), and the mixture was heated to 80° C. After theaddition of 1.0 ml (5.0 mmol) of diethyl phthalate, the mixture wasreacted for 1 hour with stirring under reflux. The resulting reactionmixture was allowed to stand, and the supernatant liquid was removed toobtain a reaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated twice. Afterthe addition of 150 ml of n-heptane (60° C.), the mixture was stirredand allowed to stand, and the supernatant liquid was removed. Thisoperation was repeated five times to wash the reaction product to obtainabout 20 g of a solid catalyst component (A6) for olefin polymerization.

The solid catalyst component (A6) had a magnesium atom content of 19.7mass %, a titanium atom content of 2.0 mass %, a halogen atom content of62.1 mass %, a total internal electron donor compound content of 12.6mass %, and a 2-ethoxyethyl ethyl carbonate content of 1.4 mass %.

Preparation of Propylene Polymerization Catalyst and Polymerization ofPropylene

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 1, except that the solidcatalyst component (A6) was used instead of the solid catalyst component(A1), and the propylene polymerization activity and the resultingpolymer were evaluated. The results are shown in Table 2.

Comparative Example 1 Synthesis of Solid Catalyst Component

A solid catalyst component was produced as described below withoutperforming the third step.

(1) First Reaction Step

A 500 ml round bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 20 ml (182 mmol) of titanium tetrachloride and 40 ml (376mmol) of toluene to prepare a solution.

A suspension prepared using 10 g (88 mmol) of sphericaldiethoxymagnesium (sphericity (l/w): 1.10) and 47 ml (442 mmol) oftoluene was added to the solution. The mixture was stirred at 4° C. for1 hour. After the addition of 2.7 ml (10.2 mmol) of di-n-butylphthalate, the mixture was heated to 105° C., and reacted for 2 hourswith stirring. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurry.

After the addition of 87 ml of toluene (100° C.) to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product. After the addition of 20 ml of titaniumtetrachloride and 80 ml of toluene, the mixture was reacted for 2 hourswith stirring. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurry.

After the addition of 87 ml of toluene (100° C.) to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product to obtain a reaction product slurryincluding a solid component (I).

(2) Second Reaction Step

20 ml (182 mmol) of titanium tetrachloride, 47 ml (442 mmol) of toluene,and 0.54 ml (2.0 mmol) of di-n-butyl phthalate were added to thereaction product slurry including the solid component (I). The mixturewas heated to 100° C., and reacted for 2 hours with stirring. Theresulting reaction mixture was allowed to stand, and the supernatantliquid was removed to obtain a reaction product slurry including a solidcomponent (II).

After the addition of 87 ml of toluene (100° C.) to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four times.After the addition of 67 ml of n-heptane (40° C.), the mixture wasstirred and allowed to stand, and the supernatant liquid was removed.This operation was repeated ten times to wash the reaction product toobtain a solid catalyst component (a1) in the form of a slurry.

The solid catalyst component (a1) had a magnesium atom content of 18.8mass %, a titanium atom content of 1.9 mass %, a halogen atom content of64.0 mass %, and a total phthalic acid diester content of 14.9 mass %.

Preparation of Olefin Polymerization Catalyst and Polymerization ofOlefin

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example1, except that the solid catalyst component (a1) was used instead of thesolid catalyst component (A1), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 1. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 2 and 3.

Comparative Example 2

A solid catalyst component (a2) was produced in the same manner as inComparative Example 1, except that 3.3 ml (13.4 mmol) of dimethyldiisobutylmalonate was used in the second step (see (2)) instead of 0.54ml (2.0 mmol) of di-n-butyl phthalate.

The solid catalyst component (a2) had a magnesium atom content of 18.6mass %, a titanium atom content of 1.5 mass %, a halogen atom content of64.9 mass %, and a total content of a phthalic acid diester and adiisobutylmalonic acid diester of 13.8 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example1, except that the solid catalyst component (a2) was used instead of thesolid catalyst component (A1), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 1. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 2 and 3.

Example 9

About 20 g of a solid catalyst component (A7) for olefin polymerizationwas produced in the same manner as in Example 1, except that 0.7 ml (3.0mmol) of di-n-propyl phthalate was used in the second step instead of0.4 ml (2.5 mmol) of 2-ethoxyethyl ethyl carbonate, and 0.7 ml (3.0mmol) of di-n-propyl phthalate was used in the third step instead of 0.4ml (2.5 mmol) of 2-ethoxyethyl ethyl carbonate.

The solid catalyst component (A7) had a magnesium atom content of 18.6mass %, a titanium atom content of 2.3 mass %, a halogen atom content of59.0 mass %, and a total phthalic acid diester content of 20.0 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example1, except that the solid catalyst component (A7) was used instead of thesolid catalyst component (A1), and 0.13 mmol or 0.24 mmol ofdicyclopentyldimethoxysilane (DCPDMS) was used instead of 0.13 mmol or0.24 mmol of cyclohexylmethyldimethoxysilane (CMDMS), and polypropyleneand an ethylene-propylene block copolymer were produced in the samemanner as in Example 1. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 2 and 3.

Example 10

About 20 g of a solid catalyst component (A8) for olefin polymerizationwas produced in the same manner as in Example 1, except that 0.8 ml (3.2mmol) of dimethyl diisobutylmalonate was used in the second step insteadof 0.4 ml (2.5 mmol) of 2-ethoxyethyl ethyl carbonate, and 0.8 ml (3.2mmol) of dimethyl diisobutylmalonate was used in the third step insteadof 0.4 ml (2.5 mmol) of 2-ethoxyethyl ethyl carbonate.

The solid catalyst component (A8) had a magnesium atom content of 19.0mass %, a titanium atom content of 2.1 mass %, a halogen atom content of60.1 mass %, a total internal electron donor compound content of 18.8mass %, and a dimethyl diisobutylmalonate content of 4.7 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example9, except that the solid catalyst component (A8) was used instead of thesolid catalyst component (A7), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 9. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 2 and 3.

Example 11

About 20 g of a solid catalyst component (A9) for olefin polymerizationwas produced in the same manner as in Example 1, except that 0.4 ml (1.8mmol) of diethyl benzylidenemalonate was used in the second step insteadof 0.4 ml (2.5 mmol) of 2-ethoxyethyl ethyl carbonate, and 0.4 ml (1.8mmol) of diethyl benzylidenemalonate was used in the third step insteadof 0.4 ml (2.5 mmol) of 2-ethoxyethyl ethyl carbonate.

The solid catalyst component (A9) had a magnesium atom content of 19.4mass %, a titanium atom content of 1.7 mass %, a halogen atom content of61.3 mass %, a total internal electron donor compound content of 16.9mass %, and a diethyl benzylidenemalonate content of 6.0 mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 1, except that the solidcatalyst component (A9) was used instead of the solid catalyst component(A1), and the propylene polymerization activity and the resultingpolymer were evaluated. The results are shown in Table 2.

Example 12 Production of Solid Catalyst Component (1) First Step

A 500 ml round-bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 120 ml (819 mmol) of n-heptane. After the addition of 15 g(158 mmol) of anhydrous magnesium chloride and 106 ml (274 mmol) oftetrabutoxytitanium, the mixture was reacted at 90° C. for 1.5 hours toobtain a homogenous solution. After cooling the solution to 40° C., 24ml (88 mmol) of methyl hydrogen polysiloxane (20 cSt) was added to thesolution, and a precipitation reaction was effected for 5 hours. Theresulting reaction mixture was allowed to stand, the supernatant liquidwas removed to obtain a reaction product slurry, and the reactionproduct was sufficiently washed with n-heptane.

A 500 ml round-bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 40 g of the reaction product, and n-heptane was added tothe flask so that the concentration of the reaction product was 200mg/ml. After the addition of 12 ml (105 mmol) of SiCl₄, the mixture wasreacted at 90° C. for 3 hours. The resulting reaction mixture wasallowed to stand, the supernatant liquid was removed to obtain areaction product slurry, and the reaction product was sufficientlywashed with n-heptane.

After the addition of n-heptane so that the concentration of thereaction product was 100 mg/ml, 20 ml (182 mmol) of TiCl₄ was added tothe mixture. After the addition of 7.2 ml (27.1 mmol) of dibutylphthalate, the mixture was reacted at 95° C. for 3 hours. The resultingreaction mixture was allowed to stand, and the supernatant liquid wasremoved to obtain a reaction product slurry.

After the addition of 120 ml of n-heptane to the reaction productslurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated seven timesto wash the reaction product to obtain a reaction product slurryincluding a solid component (I).

(2) Second Step

100 ml (695 mmol) of n-heptane was added to the reaction product slurryincluding the solid component (I). After the addition of 1.0 ml (4.4mmol) of di-n-propyl phthalate, the mixture was reacted at 95° C. for 3hours. The resulting reaction mixture was allowed to stand, and thesupernatant liquid was removed to obtain a reaction product slurryincluding a solid component (II).

(3) Third Step

187 ml (1760 mmol) of toluene and 20 ml (182 mmol) of titaniumtetrachloride were added to the reaction product slurry including thesolid component (II), and the mixture was heated. After the addition of1.0 ml (5.0 mmol) of diethyl phthalate, the mixture was reacted for 1hour with stirring under reflux. The resulting reaction mixture wasallowed to stand, and the supernatant liquid was removed to obtain areaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated twice. Afterthe addition of 150 ml of n-heptane (60° C.), the mixture was stirredand allowed to stand, and the supernatant liquid was removed. Thisoperation was repeated five times to wash the reaction product to obtainabout 20 g of a solid catalyst component (A10) for olefinpolymerization.

The solid catalyst component (A10) had a magnesium atom content of 18.9mass %, a titanium atom content of 1.8 mass %, a halogen atom content of63.6 mass %, a total carboxylic acid diester content of 15.4 mass %, anda diethyl phthalate content of 2.5 mass %.

Preparation of Polymerization Catalyst and Polymerization of Propylene

A propylene polymerization catalyst was prepared, and propylene waspolymerized in the same manner as in Example 9, except that the solidcatalyst component (A10) was used instead of the solid catalystcomponent (A7), 0.13 mmol of diethylaminotriethoxysilane (DEATES) wasused instead of 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS), andthe amount of hydrogen gas was changed from 9.01 to 6.01, and thepolymerization activity and the resulting polymer were evaluated in thesame manner as described above. The results are shown in Table 2.

Example 13

A polymerization catalyst was prepared, and propylene was polymerized inthe same manner as in Example 12 using the solid catalyst component(A10) obtained in Example 12, except that 0.13 mmol ofdicyclopentylbis(ethylamino)silane (DCPEAS) was used instead of 0.13mmol of diethylaminotriethoxysilane (DEATES), and the polymerizationactivity and the resulting polymer were evaluated in the same manner asdescribed above. The results are shown in Table 2.

TABLE 2 Polymerization NMR- activity MFR XS mmmm (kg-pp/g-cat) (g/10min) (mass %) (%) Example 1 42.2 4.0 0.6 99.1 Example 2 56.9 4.4 0.998.9 Example 3 53.5 33 0.9 99.0 Example 4 50.7 28 1.0 98.9 Example 545.5 4.9 0.7 — Example 6 55.0 5.1 0.6 99.0 Example 7 48.4 7.3 0.6 99.0Example 8 41.6 6.6 0.9 — Example 9 64.3 2.6 0.5 98.8 Example 10 56.2 5.71.0 98.6 Example 11 58.8 3.0 0.7 — Example 12 44.2 34 0.8 — Example 1348.3 39 0.7 — Comparative 57.6 29 0.9 97.7 Example 1 Comparative 63.1 460.9 97.6 Example 2

TABLE 3 Izod impact Izod impact ICP activity MFR Block ratio FM strength(23° C.) strength (−30° C.) (kg-ICP/g-cat · hr) (g/10 min) (mass %)(MPa) (J/m) (J/m) Example 1 17.0 9.3 27 1200 Did not break 7.7 Example 216.3 12 24 1250 16.5 6.7 Example 3 18.6 20 28 1050 Did not break 9.2Example 4 12.5 24 22 1400 10.5 4.6 Example 9 21.6 10 23 1300 12.0 4.8Example 10 18.3 15 23 1350 11.5 4.6 Comparative 11.3 9.8 20 1050  8.54.9 Example 1

As is clear from the results shown in Tables 2 and 3, the olefinpolymerization catalysts respectively prepared using the solid catalystcomponents obtained in Examples 1 to 13 achieved high olefinpolymerization activity and high ICP polymerization activity (i.e., highsustainability of olefin polymerization during copolymerization). Theresulting propylene polymers had a satisfactory melt flow rate (MFR)(i.e., exhibited excellent moldability), and had a satisfactoryxylene-soluble content (XS) and isotactic pentad fraction (NMR-mmmm)(i.e., exhibited excellent stereoregularity). The resulting copolymershad a satisfactory block ratio (i.e., excellent impact copolymer (ICP)copolymerization performance was achieved). The balance between rigidityand impact resistance was also improved.

Since the olefin polymerization catalysts obtained in ComparativeExamples 1 and 2 were prepared using the solid catalyst component thatwas produced without performing the second step or the third step, theresulting propylene polymers had a low xylene-soluble content (XS) and alow isotactic pentad fraction (NMR-mmmm) (i.e., exhibited inferiorstereoregularity) (see Tables 2 and 3). The olefin polymerizationcatalysts obtained in Comparative Examples 1 and 2 achieved low ICPpolymerization activity (i.e., inferior sustainability of olefinpolymerization during copolymerization), and produced a copolymer havinga low block ratio (i.e., achieved low copolymerization activity). Thebalance between the flexural modulus (FM) and the Izod impact strengthof the resulting copolymers was insufficient, (i.e., the copolymers hadinsufficient rigidity).

Example 14 Production of Solid Catalyst Component (1) First Step

A 500 ml round bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565mmol) of toluene to prepare a solution.

A suspension prepared using 20 g (175 mmol) of sphericaldiethoxymagnesium (sphericity: 1.10), 80 ml (753 mmol) of toluene, and2.2 ml (7.8 mmol) of diethyl diisobutylmalonate was added to thesolution. The mixture was stirred at −5° C. for 1 hour, and heated to110° C. 6.6 ml (23.4 mmol) of diethyl diisobutylmalonate was addedstepwise to the mixture while heating the mixture. After reacting themixture at 110° C. for 2 hours with stirring, the resulting reactionmixture was allowed to stand, and the supernatant liquid was removed toobtain a reaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product to obtain a reaction product slurryincluding a solid component (I).

(2) Second Step

Toluene was added to the reaction product slurry including the solidcomponent (I) to adjust the concentration of titanium tetrachloride inthe reaction mixture to 0.2 mass %, and the mixture was heated. Afterthe addition of 0.8 ml (3.2 mmol) of dimethyl diisobutylmalonate at 80°C., the mixture was reacted at 80° C. for 1 hour with stirring. Theresulting reaction mixture was allowed to stand, and the supernatantliquid was removed to obtain a reaction product slurry including a solidcomponent (II).

(3) Third Step

170 ml (1600 mmol) of toluene and 30 ml (273 mmol) of titaniumtetrachloride were added to the reaction product slurry including thesolid component (II). The mixture was heated to 110° C., and reacted for2 hours with stirring. After completion of the reaction, the supernatantliquid (toluene) was removed. After the addition of 180 ml of tolueneand 20 ml (182 mmol) of titanium tetrachloride, the mixture was heated.After the addition of 0.8 ml (3.2 mmol) of dimethyl diisobutylmalonateat 80° C., the mixture was heated to 110° C., and reacted for 1 hourwith stirring.

The resulting reaction mixture was allowed to stand, and the supernatantliquid was removed to obtain a reaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated twice. Afterthe addition of 150 ml of n-heptane (60° C.), the mixture was stirredand allowed to stand, and the supernatant liquid was removed. Thisoperation was repeated five times to wash the reaction product, and thesolvent component was evaporated by drying the mixture under reducedpressure to obtain about 20 g of a solid catalyst component (C1) forolefin polymerization.

The solid catalyst component (C1) had a magnesium atom content of 18.1mass %, a titanium atom content of 2.8 mass %, a halogen atom content of2.8 mass %, a total internal electron donor compound content of 18.0mass %, and a dimethyl diisobutylmalonate content of 6.5 mass %.

Preparation of Propylene Polymerization Catalyst and Polymerization ofPropylene

An autoclave (internal volume: 2.0 l) equipped with a stirrer in whichthe internal atmosphere had been completely replaced by nitrogen gas,was charged with 1.32 mmol of triethylaluminum, 0.13 mmol ofdicyclopentyldimethoxysilane (DCPDMS), and the solid catalyst component(C1) (0.0013 mmol on a titanium atom basis) to prepare an olefinpolymerization catalyst.

The autoclave was charged with 1.5 l of hydrogen gas and 1.4 l ofliquefied propylene. The liquefied propylene was subjected topreliminary polymerization at 20° C. for 5 minutes under a pressure of1.1 MPa, heated, and polymerized at 70° C. for 1 hour under a pressureof 3.5 MPa to obtain a propylene polymer (polypropylene).

The polymerization activity per gram of the solid catalyst component,the p-xylene-soluble content (XS) in the polymer, the melt flow rate(MFR) of the polymer, the isotactic pentad fraction (NMR-mmmm) of thepolymer, and the flexural modulus (FM) of the polymer were measured asdescribed above. The results are shown in Table 4.

Preparation of Copolymerization Catalyst and Ethylene-Propylene BlockCopolymerization

A copolymerization catalyst was prepared as described below using thesolid catalyst component, and a copolymer was produced by multisteppolymerization as described below. The ethylene-propylene blockcopolymerization activity (ICP (impact copolymer) activity) duringcopolymerization was measured to evaluate the sustainability ofpolymerization activity, and the melt flow rate (MFR), the block ratio,the flexural modulus (FM), and the Izod impact strength of the resultingethylene-propylene block copolymer were measured.

An autoclave (internal volume: 2.0 l) equipped with a stirrer in whichthe internal atmosphere had been completely replaced by nitrogen gas,was charged with 2.4 mmol of triethylaluminum, 0.24 mmol ofdicyclopentyldimethoxysilane (DCPDMS), and the solid catalyst component(C1) (0.003 mmol on a titanium atom basis) to prepare anethylene-propylene copolymerization catalyst (D1).

The autoclave containing the ethylene-propylene copolymerizationcatalyst (D1) was charged with liquefied propylene (15 mol) and hydrogengas (partial pressure: 0.20 MPa). The liquefied propylene was subjectedto preliminary polymerization at 20° C. for 5 minutes, and subjected tofirst-step propylene polymerization (homopolymerization) at 70° C. for75 minutes. The pressure inside the autoclave was then returned tonormal pressure.

After feeding ethylene, propylene, and hydrogen to the autoclave in amolar ratio of 1.0/1.0/0.043, the mixture was heated to 70° C., andreacted at 70° C. for 1 hour under a pressure of 1.2 MPa while feedingethylene, propylene, and hydrogen in a ratio of 2/2/0.086 (I/min) toobtain an ethylene-propylene copolymer.

The ethylene-propylene block copolymerization activity (ICP activity)(g-ICP/(g-cat·hr)), the melt flow rate (MFR), the block ratio (mass %),the flexural modulus (FM), and the Izod impact strength of theethylene-propylene copolymer were measured as described above. Theresults are shown in Table 5.

Example 15

About 20 g of a solid catalyst component (C2) for olefin polymerizationwas produced in the same manner as in Example 14, except that the amountof diethyl diisobutylmalonate added stepwise in the first step waschanged from 6.6 ml (23.4 mmol) to 5.9 ml (21.1 mmol), the amount ofdimethyl diisobutylmalonate added in the second step was changed from0.8 ml (3.2 mmol) to 0.4 ml (1.6 mmol), and the amount of dimethyldiisobutylmalonate added in the third step was changed from 0.8 ml (3.2mmol) to 0.4 ml (1.6 mmol).

The solid catalyst component (C2) had a magnesium atom content of 18.3mass %, a titanium atom content of 2.9 mass %, a halogen atom content of61.1 mass %, a total internal electron donor compound content of 17.1mass %, and a dimethyl diisobutylmalonate content of 3.1 mass %.

A propylene polymerization catalyst was prepared, and polypropylene wasproduced in the same manner as in Example 14, except that the solidcatalyst component (C2) was used instead of the solid catalyst component(C1), and the propylene polymerization activity and the resultingpolymer were evaluated.

The results are shown in Table 4.

Example 16

About 20 g of a solid catalyst component (C3) for olefin polymerizationwas produced in the same manner as in Example 14, except that diethylbenzylidenemalonate (equimolar amount) was used in the first stepinstead of diethyl diisobutylmalonate, diethyl benzylidenemalonate(equimolar amount) was used in the second step instead of dimethyldiisobutylmalonate, and diethyl benzylidenemalonate (equimolar amount)was used in the third step instead of dimethyl diisobutylmalonate.

The solid catalyst component (C3) had a magnesium atom content of 21.3mass %, a titanium atom content of 1.9 mass %, a halogen atom content of64.6 mass %, and a total diethyl benzylidenemalonate content of 10.5mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example14, except that the solid catalyst component (C3) was used instead ofthe solid catalyst component (C1), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 14. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 4 and 5.

Example 17 Production of Solid Catalyst Component

About 20 g of a solid catalyst component (C4) for olefin polymerizationwas produced in the same manner as in Example 14, except that thesuspension was prepared in the first step using a mixture of 1.1 ml (3.9mmol) of diethyl diisobutylmalonate and 0.9 ml (4.0 mmol) of diethylbenzylidenemalonate instead of 2.2 ml (7.8 mmol) of diethyldiisobutylmalonate, a mixture of 0.2 ml (0.7 mmol) of diethyldiisobutylmalonate and 0.2 ml (0.9 mmol) of diethyl benzylidenemalonatewas used in the second step instead of 0.8 ml (3.2 mmol) of dimethyldiisobutylmalonate, and a mixture of 0.2 ml (0.7 mmol) of diethyldiisobutylmalonate and 0.2 ml (0.9 mmol) of diethyl benzylidenemalonatewas used in the third step instead of 0.8 ml (3.2 mmol) of dimethyldiisobutylmalonate.

The solid catalyst component (C4) had a magnesium atom content of 21.0mass %, a titanium atom content of 2.1 mass %, a halogen atom content of64.1 mass %, a total internal electron donor compound content of 11.9mass %, and a diethyl benzylidenemalonate content of 3.9 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example14, except that the solid catalyst component (C4) was used instead ofthe solid catalyst component (C1), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 14. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 4 and 5.

Example 18

About 20 g of a solid catalyst component (C5) for olefin polymerizationwas produced in the same manner as in Example 14, except that2-ethoxyethyl ethyl carbonate (equimolar amount) was used in the firststep instead of diethyl diisobutylmalonate.

The solid catalyst component (C5) had a magnesium atom content of 21.9mass %, a titanium atom content of 1.7 mass %, a halogen atom content of63.9 mass %, a total internal electron donor compound content of 11.5mass %, and a dimethyl diisobutylmalonate content of 6.5 mass %.

A propylene polymerization catalyst was prepared, and propylene waspolymerized in the same manner as in Example 14, except that the solidcatalyst component (C5) was used instead of the solid catalyst component(C1), and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 4.

Example 19

About 20 g of a solid catalyst component (C6) for olefin polymerizationwas produced in the same manner as in Example 14, except that the firstinternal electron donor compound added in the first step was changedfrom 8.8 ml (31.2 mmol) (in total) of diethyl diisobutylmalonate to 5.3ml (20.8 mmol) (in total) of 3,3-bis(methoxymethyl)-2,6-dimethylheptane,and 0.4 ml (1.8 mmol) of diethyl benzylidenemalonate was used in thesecond step and the third step instead of 0.8 ml (3.2 mmol) of dimethyldiisobutylmalonate.

The solid catalyst component (C6) had a magnesium atom content of 21.6mass %, a titanium atom content of 2.1 mass %, a halogen atom content of63.3 mass %, a total internal electron donor compound content of 12.6mass %, and a diethyl benzylidenemalonate content of 3.2 mass %.

A propylene polymerization catalyst was prepared, and propylene waspolymerized in the same manner as in Example 14, except that the solidcatalyst component (C6) was used instead of the solid catalyst component(C1), and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 4.

Comparative Example 3

About 20 g of a solid catalyst component (c1) for olefin polymerizationwas produced in the same manner as in Example 14, except that 1.6 ml(6.5 mmol) of dimethyl diisobutylmalonate was used in the second stepinstead of 0.8 ml (3.2 mmol) of dimethyl diisobutylmalonate, and thethird step was not performed.

The solid catalyst component (c1) had a magnesium atom content of 16.4mass %, a titanium atom content of 4.2 mass %, a halogen atom content of59.0 mass %, a total internal electron donor compound content of 20.1mass %, and a dimethyl diisobutylmalonate content of 7.4 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example14, except that the solid catalyst component (c1) was used instead ofthe solid catalyst component (C1), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 14. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 4 and 5.

Comparative Example 4

About 20 g of a solid catalyst component (c2) for olefin polymerizationwas produced in the same manner as in Example 14, except that 1.6 ml(6.5 mmol) of dimethyl diisobutylmalonate was used in the third stepinstead of 0.8 ml (3.2 mmol) of dimethyl diisobutylmalonate, and thesecond step was not performed.

The solid catalyst component (c2) had a magnesium atom content of 17.4mass %, a titanium atom content of 3.7 mass %, a halogen atom content of59.5 mass %, a total internal electron donor compound content of 19.2mass %, and a dimethyl diisobutylmalonate content of 6.4 mass %.

Polypropylene and an ethylene-propylene block copolymer were produced inthe same manner as in Example 14, except that the solid catalystcomponent (c2) was used instead of the solid catalyst component (C1),and the propylene polymerization activity, the ethylene-propylene blockcopolymerization activity (ICP activity), and the resulting polymerswere evaluated in the same manner as described above. The results areshown in Table 4.

Example 20 Production of Solid Catalyst Component (1) First Step

A 500 ml round bottom flask equipped with a stirrer in which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565mmol) of toluene to prepare a solution.

A suspension prepared using 20 g (175 mmol) of sphericaldiethoxymagnesium (sphericity (l/w): 1.10), 80 ml (753 mmol) of toluene,and 1.9 ml (7.7 mmol) of dimethyl diisobutylmalonate was added to thesolution. The mixture was stirred at −5° C. for 1 hour, and heated to110° C. 5.7 ml (23.1 mmol) of dimethyl diisobutylmalonate was addedstepwise to the mixture while heating the mixture. After reacting themixture at 110° C. for 2 hours with stirring, the resulting reactionmixture was allowed to stand, and the supernatant liquid was removed toobtain a reaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product. After the addition of 170 ml (1600 mmol)of toluene and 30 ml (273 mmol) of titanium tetrachloride, the mixturewas heated to 110° C., and reacted for 2 hours with stirring. Theresulting reaction mixture was allowed to stand, and the supernatantliquid was removed to obtain a reaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated four timesto wash the reaction product to obtain a reaction product slurryincluding a solid component (I).

(2) Second Step

Toluene was added to the reaction product slurry including the solidcomponent (I) to adjust the concentration of titanium tetrachloride inthe reaction mixture to 0.2 mass %, and the mixture was heated. Afterthe addition of 0.4 ml (2.5 mmol) of 2-ethoxyethyl ethyl carbonate at80° C., the mixture was reacted at 100° C. for 1 hour with stirring. Theresulting reaction mixture was allowed to stand, and the supernatantliquid was removed to obtain a reaction product slurry including a solidcomponent (II).

(3) Third Step

170 ml (1600 mmol) of toluene and 30 ml (273 mmol) of titaniumtetrachloride were added to the reaction product slurry including thesolid component (II). The mixture was heated to 110° C., and reacted for1 hour with stirring. After completion of the reaction, the supernatantliquid (toluene) was removed. After the addition of 180 ml of tolueneand 20 ml (182 mmol) of titanium tetrachloride, the mixture was heated.After the addition of 0.8 ml (3.2 mmol) of dimethyl diisobutylmalonateat 80° C., the mixture was heated to 110° C., and reacted for 2 hourswith stirring. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed to obtain a reaction product slurry.

After the addition of 187 ml of toluene (100° C.) to the reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated twice. Afterthe addition of 150 ml of n-heptane (60° C.) to the resulting reactionproduct slurry, the mixture was stirred and allowed to stand, and thesupernatant liquid was removed. This operation was repeated five timesto wash the reaction product to obtain about 20 g of a solid catalystcomponent (C7) for olefin polymerization.

The solid catalyst component (C7) had a magnesium atom content of 18.9mass %, a titanium atom content of 2.1 mass %, a halogen atom content of61.6 mass %, a total internal electron donor compound content of 16.1mass %, and a dimethyl diisobutylmalonate content of 14.5 mass %.

Preparation of Olefin Polymerization Catalyst and Evaluation ofPolymerization

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example14, except that the solid catalyst component (C7) was used instead ofthe solid catalyst component (C1), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 14. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 4 and 5.

Example 21

About 20 g of a solid catalyst component (C8) was produced in the samemanner as in Example 20, except that diethyl diisobutylmalonate(equimolar amount) was used in the first step instead of dimethyldiisobutylmalonate.

The solid catalyst component (C8) had a magnesium atom content of 18.6mass %, a titanium atom content of 2.2 mass %, a halogen atom content of60.8 mass %, a total internal electron donor compound content of 16.3mass %, a diethyl diisobutylmalonate content of 1.5 mass %, and a2-ethoxyethyl ethyl carbonate content of 1.1 mass %.

A propylene polymerization catalyst was prepared, and propylene waspolymerized in the same manner as in Example 14, except that the solidcatalyst component (C8) was used instead of the solid catalyst component(C1), and the polymerization activity and the resulting polymer wereevaluated. The results are shown in Table 4.

TABLE 4 Polymerization NMR- activity MFR XS mmmm FM (kg-pp/g-cat) (g/10min) (mass %) (%) (MPa) Example 14 54.0 16 1.8 97.4 1510 Example 15 59.613 1.9 — — Example 16 49.7 1.8 1.2 97.7 1460 Example 17 51.5 13 1.5 97.51500 Example 18 44.2 4.3 0.6 — — Example 19 50.4 4.9 0.7 — — Example 2046.6 25 1.3 97.7 1540 Example 21 51.3 15 1.5 — — Comparative 38.3 60 3.395.5 1420 Example 3 Comparative 18.4 58 3.5 95.3 1460 Example4

TABLE 5 Izod impact Izod impact ICP activity MFR Block ratio FM strength(23° C.) strength (−30° C.) (kg-ICP/g-cat · hr) (g/10 min) (mass %)(MPa) (J/m) (J/m) Example 14 15.9 12 24 1050 16.9 6.3 Example 16 11.1 822 1100 11.5 5.7 Example 17 14.1 10 23 1050 12.8 5.9 Example 20 13.8 2626 1070 Did not break 7.5 Comparative 7.9 24 18 1120 7.2 3.9 Example 3Comparative 5.6 26 19 1090 8.0 4.1 Example 4

Example 22

A solid catalyst component (C9) was produced in the same manner as inExample 14, except that dimethyl diisobutylmalonate (equimolar amount)was added in the first step as the first internal electron donorcompound instead of diethyl diisobutylmalonate, diethyl maleate(equimolar amount) was added in the second step as the second internalelectron donor compound instead of dimethyl diisobutylmalonate, anddiethyl maleate (equimolar amount) was added in the third step as thethird internal electron donor compound instead of dimethyldiisobutylmalonate.

The solid catalyst component (C9) had a magnesium atom content of 19.3mass %, a titanium atom content of 2.4 mass %, a halogen atom content of60.3 mass %, a total internal electron donor compound (carboxylic aciddiester compound) content of 14.9 mass %, and a diethyl maleate contentof 4.1 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example9, except that the solid catalyst component (C9) was used instead of thesolid catalyst component (A7), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 9. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 6 and 7.

Example 23

A solid catalyst component (C10) was produced in the same manner as inExample 1, except that diethyl cyclohexene-1,2-dicarboxylate (equimolaramount) was added in the first step as the first internal electron donorcompound instead of di-n-propyl phthalate, diethylcyclohexene-1,2-dicarboxylate (equimolar amount) was added in the secondstep as the second internal electron donor compound instead of2-ethoxyethyl ethyl carbonate, and diethyl cyclohexene-1,2-dicarboxylate(equimolar amount) was added in the third step as the third internalelectron donor compound instead of 2-ethoxyethyl ethyl carbonate.

The solid catalyst component (C10) had a magnesium atom content of 19.4mass %, a titanium atom content of 2.2 mass %, a halogen atom content of60.0 mass %, and a total internal electron donor compound (carboxylicacid diester compound) content of 13.3 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example9, except that the solid catalyst component (C10) was used instead ofthe solid catalyst component (A7), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 9. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 6 and 7.

Example 24

A solid catalyst component (C11) was produced in the same manner as inExample 1, except that dipropyl cyclohexene-1,2-dicarboxylate (equimolaramount) was added in the first step as the first internal electron donorcompound instead of di-n-propyl phthalate, dipropylcyclohexene-1,2-dicarboxylate (equimolar amount) was added in the secondstep as the second internal electron donor compound instead of2-ethoxyethyl ethyl carbonate, and dipropylcyclohexene-1,2-dicarboxylate (equimolar amount) was added in the thirdstep as the third internal electron donor compound instead of2-ethoxyethyl ethyl carbonate.

The solid catalyst component (C11) had a magnesium atom content of 19.8mass %, a titanium atom content of 2.5 mass %, a halogen atom content of60.1 mass %, and a total internal electron donor compound (carboxylicacid diester compound) content of 11.9 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example9, except that the solid catalyst component (C11) was used instead ofthe solid catalyst component (A7), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 9. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 6 and 7.

Example 25

A solid catalyst component (C12) was produced in the same manner as inExample 9, except that the second step was performed as described below.Specifically, toluene was added to the reaction product slurry includingthe solid component obtained by the first step to adjust theconcentration of titanium tetrachloride in the reaction mixture to 0.2mass %, and the mixture was heated while adding 0.7 ml (3.0 mmol) ofdi-n-propyl phthalate. The mixture was reacted at 100° C. for 1 hourwith stirring. The resulting reaction mixture was allowed to stand, andthe supernatant liquid was removed. Toluene was added to the reactionproduct slurry to adjust the concentration of titanium tetrachloride inthe reaction mixture to 0.1 mass % to obtain a reaction productincluding a solid component.

The solid catalyst component (C12) had a magnesium atom content of 20.2mass %, a titanium atom content of 1.9 mass %, a halogen atom content of59.6 mass %, and a total internal electron donor compound (carboxylicacid diester compound) content of 18.9 mass %.

A propylene polymerization catalyst and an ethylene-propylenecopolymerization catalyst were prepared in the same manner as in Example9, except that the solid catalyst component (C12) was used instead ofthe solid catalyst component (A7), and polypropylene and anethylene-propylene block copolymer were produced in the same manner asin Example 9. The propylene polymerization activity, theethylene-propylene block copolymerization activity (ICP activity), andthe resulting polymers were evaluated in the same manner as describedabove. The results are shown in Tables 6 and 7.

TABLE 6 Polymerization NMR- activity MFR XS mmmm FM (kg-pp/g-cat) (g/10min) (mass %) (%) (MPa) Example 22 47.2 13 1.3 97.8 1550 Example 23 51.22.5 0.9 98.1 1570 Example 24 56.1 3.0 1.2 97.7 1550 Example 25 66.4 2.40.4 98.9 1590

TABLE 7 ICP activity Block ratio (g-pp/g-cat) (mass %) Example 22 13.925 Example 23 17.3 27 Example 24 15.7 26 Example 25 22.6 25

As is clear from the results shown in Tables 4 to 7, the olefinpolymerization catalysts respectively prepared using the solid catalystcomponents obtained in Examples 14 to 25 achieved high olefinpolymerization activity and good activity (response) with respect tohydrogen during polymerization, and achieved high ICP activity (i.e.,high sustainability of olefin polymerization during copolymerization).The resulting polymers had a satisfactory melt flow rate (MFR) (i.e.,exhibited excellent moldability), had a satisfactory xylene-solublecontent (XS) and isotactic pentad fraction (NMR-mmmm) (i.e., exhibitedexcellent stereoregularity), and had a satisfactory flexural modulus(FM) (i.e., exhibited excellent physical strength such as rigidity). Theresulting copolymers had a satisfactory block ratio (i.e., excellentimpact copolymer (ICP) copolymerization performance was achieved).

Since the olefin polymerization catalysts obtained in ComparativeExamples 3 and 4 were prepared using the solid catalyst component thatwas produced without performing the second step or the third step, theolefin polymerization activity was low, or the resulting polymer had aninferior isotactic pentad fraction (NMR-mmmm) (i.e., exhibited lowstereoregularity), or the impact copolymer (ICP) had a low Izod impactstrength (see Tables 4 and 5).

INDUSTRIAL APPLICABILITY

The embodiments of the invention thus provide a method for producing anovel solid catalyst component for olefin polymerization that achievesexcellent olefin polymerization activity and activity with respect tohydrogen during polymerization when homopolymerizing or copolymerizingan olefin, and can produce an olefin homopolymer or copolymer thatexhibits a high MFR and excellent stereoregularity while achieving highsustainability of polymerization activity, and also provide a novelolefin polymerization catalyst and a method for producing an olefinpolymer.

1. A method for producing a solid catalyst component for olefin polymerization comprising: a first step that brings a magnesium compound, a tetravalent titanium halide compound, and one or more first internal electron donor compounds into contact with each other to effect a reaction, followed by washing; a second step that brings one or more second internal electron donor compounds into contact with a product obtained by the first step without adding a tetravalent titanium halide compound so that a relationship “molar quantity of the first internal electron donor compound>molar quantity of the second internal electron donor compound” is satisfied, to effect a reaction; and a third step that brings a tetravalent titanium halide compound and one or more third internal electron donor compounds into contact with a product obtained by the second step so that a relationship “molar quantity of the second internal electron donor compound≧molar quantity of the third internal electron donor compound” is satisfied, to effect a reaction.
 2. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the second internal electron donor compound is used so that a ratio “molar quantity of the second internal electron donor compound/molar quantity of the magnesium compound” is 0.001 to
 10. 3. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the third internal electron donor compound is used so that a ratio “molar quantity of the third internal electron donor compound/molar quantity of the magnesium compound” is 0.001 to
 10. 4. (canceled)
 5. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the second internal electron donor compound is brought into contact with the product obtained by the first step in an inert organic solvent for which a tetravalent titanium halide compound content is controlled to 0 to 5 mass %.
 6. An olefin polymerization catalyst produced by bringing a solid catalyst component for olefin polymerization obtained by the method for producing a solid catalyst component for olefin polymerization according to claim 1, an organoaluminum compound represented by a general formula (I), and an external electron donor compound into contact with each other, R¹AlQ_(3-p)  (I) wherein R¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is a real number that satisfies 0<p≦3.
 7. The olefin polymerization catalyst according to claim 6, wherein the external electron donor compound is one or more organosilicon compounds selected from an organosilicon compound represented by a general formula (II) and an organosilicon compound represented by a general formula (III), R² _(q)Si(OR³)_(4-q)  (II) wherein R² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, provided that a plurality of R² are either identical or different when a plurality of R² are present, R³ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, provided that a plurality of R³ are either identical or different when a plurality of R³ are present, and q is an integer from 0 to 3, (R⁴R⁵N)_(s)SiR⁶ _(4-s)  (III) wherein R⁴ and R⁵ are a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group, provided that R⁴ and R⁵ are either identical or different, and optionally bond to each other to form a ring, R⁶ is a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms, a vinyloxy group, an allyloxy group, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, or an aryloxy group, provided that a plurality of R⁶ are either identical or different when a plurality of R⁶ are present, and s is an integer from 1 to
 3. 8. A method for producing an olefin polymer comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim
 6. 9. A method for producing an olefin polymer comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim
 7. 